Dielectric ceramic composition and ceramic electronic components

ABSTRACT

Provided is a dielectric ceramic composition including a first component and a second component, wherein the first component comprises an oxide of Ca of 0.00 mol % to 35.85 mol % an oxide of Sr of 0.00 mol % to 47.12 mol %, an oxide of Ba of 0.00 mol % to 51.22 mol %, an oxide of Ti of 0.00 mol % to 17.36 mol %, an oxide of Zr of 0.00 mol % to 17.36 mol %, an oxide of Sn of 0.00 mol % to 2.60 mol %, an oxide of Nb of 0.00 mol % to 35.32 mol %, an oxide of Ta of 0.00 mol % to 35.32 mol %, and an oxide of V of 0.00 mol % to 2.65 mol %, and the second component includes at least (a) an oxide of Mn of 0.005% by mass to 3.500% by mass and (b) an oxide of Cu and/or an oxide of Ru.

TECHNICAL FIELD

The present invention relates to a dielectric ceramic composition andceramic electronic components using the dielectric ceramic compositionas a dielectric layer.

BACKGROUND ART

In recent years, requirements of electronic components that are operatedunder a high temperature environment exceeding 150° C. have increasedyear by year for devices mounted in a harsh temperature environment,such as an environment around an engine room of an automobile. Inparticular, in an automobile market in recent years, the use ofelectronic control for each function has rapidly progressed, aiming atimproving safety and environmental performance. Consequently, themounting ratio of electronic devices has been increased. Of theseelectronic devices, an electronic device mounted in an engine room isexposed to a harsh temperature environment and thus high heat resistancein addition to high reliability has been required for the electroniccomponents.

Conventionally, as the ceramic electronic components satisfying suchrequirement such as capacitors, a ceramic composition exhibiting aparaelectricity (paraelectric material) such as calcium zirconate isused for a dielectric layer of the ceramic electronic components.However, the electronic components having a dielectric layer constitutedby the paraelectric material have low relative dielectric constant ofthe ceramic composition and thus capacitors having high capacity cannotbe obtained.

Barium titanate (BaTiO₃) known as a representative ceramic compositionfor ceramic capacitors has a high relative dielectric constant. However,barium titanate has the peak of the relative dielectric constant at acharacteristic temperature referred to as a ferroelectric transitiontemperature and the properties are rapidly lowered at 120° C. or more.

Therefore, the development of a dielectric ceramic composition having ahigh relative dielectric constant even in a high temperature environment(for example, 150° C. or more) has been desired.

In recent years, in the ceramic electronic components, a base metal suchas nickel and copper is frequently used as a material for internalelectrodes. In the case where the base metal is used as the internalelectrode layer, the dielectric layer and the internal electrodes areco-fired. In order to prevent the base metal from oxidation duringfiring, the ceramic electronic components including the ceramiccomposition constituting the dielectric layer are fired under a reducingatmosphere.

Non-Patent Literature 1 has described a dielectric ceramic compositionhaving a tungsten bronze structure represented by a general formula M²⁺₆M⁴⁺ ₂Nb₈O₃₀. In this Non-Patent Literature 1, in order to obtainexperimental samples, the raw materials of the ceramic composition aremixed, and thereafter the materials are fired around 1,000° C. for 15hours. The obtained product is ground, dried, and molded, and thereafterfurther sintered at 1,250° C. to 1,350° C. for 5 hours to 6 hours.

In Patent Literatures 1 to 11, the dielectric ceramic compositionshaving various tungsten bronze structures have been studied.

CITATION LIST Non-Patent Literature

-   Non-Patent Literature 1: Mat. Res. Bull., Vol. 27 (1992), pp.    677-684; R. R. Neurgaonkar, J. G. Nelson and J. R. Oliver

Patent Literatures

-   Patent Literature 1: Japanese Patent Application Laid-open No.    2002-211975-   Patent Literature 2: Japanese Patent Application Laid-open No.    2007-197277-   Patent Literature 3: Japanese Patent Application Laid-open No.    H11-043370-   Patent Literature 4: Japanese Patent Application Laid-open No.    2000-169215-   Patent Literature 5: Japanese Patent Application Laid-open No.    2008-189487-   Patent Literature 6: WO 08/102608 Pamphlet-   Patent Literature 7: WO 06/114914 Pamphlet-   Patent Literature 8: Japanese Patent Application Laid-open No.    2013-180906-   Patent Literature 9: Japanese Patent Application Laid-open No.    2013-180907-   Patent Literature 10: Japanese Patent Application Laid-open No.    2013-180908-   Patent Literature 11: Japanese Patent Application Laid-open No.    2012-169635

SUMMARY Technical Problem

However, in Non-Patent Literature 1, although the properties of thedielectric ceramic composition itself having the tungsten bronzestructure have been studied from the academic viewpoint, theapplications of the dielectric ceramic composition are not considered atall. In other words, in Non-Patent Literature 1, the dielectric ceramiccomposition is fired in a laboratory under a normal environmentalatmosphere. However, as a result of detailed study for the dielectricceramic composition having the tungsten bronze structure represented bythe general formula conducted by the inventors of the present invention,the inventors of the present invention have found that a dielectricceramic composition having completely different properties from those ofthe dielectric ceramic composition reported in Non-Patent Literature 1is obtained in the case where firing and sintering are performed under areducing atmosphere that has been required for dielectric ceramiccompositions in recent years.

In Patent Literatures 1 to 11, the dielectric ceramic compositionshaving the tungsten bronze structures have also been studied. However,in any of these Patent Literatures, dielectric ceramic compositionssimultaneously exhibiting the effects of “being possible to be firedunder a reducing atmosphere”, “providing sufficiently a high relativedielectric constant”, “having an excellent dielectric property in a widetemperature region”, and “having a small dielectric loss” have not beenobtained.

In addition to the above-described performances, for the dielectricceramic composition, a high insulation resistance value above a certainlevel (for example, about 40 MΩ at 200° C.) is required for electroniccomponents using the dielectric ceramic composition.

Therefore, an object of the present invention is to provide a dielectricceramic composition that can be fired under a reducing atmosphere, has ahigh relative dielectric constant, and, in the case where the dielectricceramic composition is used as the dielectric layer of ceramicelectronic components such as a laminated ceramic capacitor, has a smallchange in electrostatic capacity even under a high temperatureenvironment, for example, under a condition of 150° C. to 200° C. andsmall dielectric losses at 25° C. and 200° C., and further can obtain ahigh insulation resistance value even at 200° C., and ceramic electroniccomponents in which the dielectric ceramic composition is used as thedielectric layer.

Solution to Problem

The above-described problems are solved by the present inventiondescribed below.

Namely, the present invention (1) provides a dielectric ceramiccomposition comprising: a first component; and a second component,wherein

as a content ratio relative to a total number of moles of the firstcomponent when converted into following oxides, the first componentcomprises an oxide of Ca of 0.00 mol % to 35.85 mol % in terms of CaO,an oxide of Sr of 0.00 mol % to 47.12 mol % in terms of SrO, an oxide ofBa of 0.00 mol % to 51.22 mol % in terms of BaO, an oxide of Ti of 0.00mol % to 17.36 mol % in terms of TiO₂, an oxide of Zr of 0.00 mol % to17.36 mol % in terms of ZrO₂, an oxide of Sn of 0.00 mol % to 2.60 mol %in terms of SnO₂, an oxide of Nb of 0.00 mol % to 35.32 mol % in termsof Nb₂O₅, an oxide of Ta of 0.00 mol % to 35.32 mol % in terms of Ta₂O₅,and an oxide of V of 0.00 mol % to 2.65 mol % in terms of V₂O₅;

the first component comprises at least one oxide selected from the oxideof Ca, the oxide of Sr, and the oxide of Ba, at least one oxide selectedfrom the oxide of Ti and the oxide of Zr, and at least one oxideselected from the oxide of Nb and the oxide of Ta as essentialcomponents, and, a total content ratio of the oxide of Ca in terms ofCaO, the oxide of Sr in terms of SrO, and the oxide of Ba in terms ofBaO is 48.72 mol % to 51.22 mol %, a total content ratio of the oxide ofTi in terms of TiO₂, the oxide of Zr in terms of ZrO₂, and the oxide ofSn in terms of SnO₂ is 15.97 mol % to 17.36 mol %, and a total contentratio of the oxide of Nb in terms of Nb₂O₅, the oxide of Ta in terms ofTa₂O₅, and the oxide of V in terms of V₂O₅ is 31.42 mol % to 35.31 mol %relative to the total number of moles of the first component whenconverted into the oxides; and

as a content ratio relative to a total mass of the first component whenconverted into the oxides, the second component comprises at least (a)an oxide of Mn of 0.005% by mass to 3.500% by mass in terms of MnO and(b) one or both of an oxide of Cu and an oxide of Ru.

In addition, the present invention (2) provides a dielectric ceramiccomposition comprising: a first component; and a second component,wherein

as the first component, a compound represented by a following generalformula (1):

A_(a)M¹ _(b)M² _(c)O_(d)  (1)

(in the formula (1), A is represented by a general formula (2):

Ba_(1-x-y)Sr_(x)Ca_(y)  (2)

(in the formula (2), 0≤x≤0.920 and 0≤y≤0.700); M¹ is at least oneelement selected from Ti, Zr, and Sn; M² is at least one elementselected from Nb, Ta, and V; and 5.70≤a≤6.30, 1.90≤b≤2.10, 7.20≤c≤8.80,and 27.45≤d≤32.50) is included (with the proviso that, when Sn isincluded, a content ratio of the oxide of Sn in terms of SnO₂ relativeto a total number of moles of the oxide of Ti in terms of TiO₂, theoxide of Zr in terms of ZrO₂, and the oxide of Sn in terms of SnO₂ is15.00 mol % or less and when V is included, a content ratio of the oxideof V in terms of V₂O₅ relative to a total number of moles of the oxideof Nb in terms of Nb₂O₅, the oxide of Ta in terms of Ta₂O₅, and theoxide of V in terms of V₂O₅ is 7.50 mol % or less); and

as a content ratio relative to a total mass of the first component whenthe first component is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂,Nb₂O₅, Ta₂O₅, and V₂O₅, the second component comprises at least (a) anoxide of Mn of 0.005% by mass to 3.500% by mass in terms of MnO and (b)one or both of an oxide of Cu and an oxide of Ru.

In addition, the present invention (3) provides a dielectric ceramiccomposition comprising: a first component; and a second component,wherein

a compound represented by a following general formula (3):

α·Ca_(η1)M³ _(θ1)M⁴ _(ϕ1)O_(ω1)-β·Sr_(η2)M³ _(θ2)M⁴_(ϕ2)O_(ω2-γ)·Ba_(η3)M³ _(θ3)M⁴ _(ϕ3)O_(ω3)  (3)

(in the formula (3), η1, η2, and η3 are each independently values withina range of 5.70 to 6.30; θ1, θ2, and θ3 are each independently valueswithin a range of 0.95 to 1.05; ϕ1, ϕ2, and ϕ3 are each independentlyvalues within a range of 0.90 to 1.10; ω1, ω2, and ω3 are eachindependently values within a range of 27.45 to 32.50; M³ is representedby a general formula (4):

Ti_(2-ρ-σ)Zr_(ρ)Sn_(σ)  (4)

(in the formula (4), 0≤ρ≤2.0 and 0≤σ≤0.3); M⁴ is represented by ageneral formula (5):

Nb_(8-π-ψ)Ta_(π)V_(ψ)  (5)

(in the formula (5), 0≤π≤8.0 and 0≤ψ≤0.6); and α, β, and γ satisfyα+β+γ=1.00), and when an arbitrary point in a ternary compositiondiagram is represented as (α, β, γ), the compound existing within arange surrounded by line segments linking a point A=(0.05, 0.95, 0.00),a point B=(0.70, 0.30, 0.00), a point C=(0.70, 0.00, 0.30), a pointD=(0.00, 0.00, 1.00), and a point E=(0.00, 0.90, 0.10) is included asthe first component, and

as a content ratio relative to a total mass of the first component whenthe first component is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂,Nb₂O₅, Ta₂O₅, and V₂O₅, the second component comprises at least (a) anoxide of Mn of 0.005% by mass to 3.500% by mass in terms of MnO and (b)one or both of an oxide of Cu and an oxide of Ru.

In addition, the present invention (4) provides the dielectric ceramiccomposition of (3), wherein the first component is a compound existingwithin a range surrounded by line segments linking a point A′=(0.05,0.95, 0.00), a point B′=(0.60, 0.40, 0.00), a point C′=(0.70, 0.20,0.10), a point D′=(0.70, 0.10, 0.20), a point E′=(0.55, 0.00, 0.45), apoint F′=(0.40, 0.00, 0.60), a point G′=(0.10, 0.10, 0.80), a pointH′=(0.00, 0.00, 1.00), a point I′=(0.00, 0.40, 0.60) a point J′=(0.20,0.40, 0.40), a point K′=(0.00, 0.70, 0.30), and a point L′=(0.00, 0.90,0.10) in the ternary composition diagram.

In addition, the present invention (5) is the dielectric ceramiccomposition according to any one of (1) to (4), wherein, as the contentratio relative to the total mass of the first component when the firstcomponent is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅,Ta₂O₅, and V₂O₅, the second component comprises one or both of an oxideof Cu of 0.010% by mass or more and less than 0.080% by mass in terms ofCuO and an oxide of Ru of 0.050% by mass or more and less than 0.300% bymass in terms of RuO₂.

In addition, the present invention (6) provides the dielectric ceramiccomposition of any one of (1) to (5), wherein an oxide of D (D is atleast one element selected from Li, Mg, Si, Cr, Al, Fe, Co, Ni, Zn, Ga,Ge, In, W, Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,Yb, and Lu) is included as the second component.

In addition, the present invention (7) provides the dielectric ceramiccomposition of any one of (1) to (6), wherein the dielectric ceramiccomposition comprises a tungsten bronze type crystal phase.

In addition, the present invention (8) provides the dielectric ceramiccomposition of any one of (1) to (7), wherein the relative dielectricconstant at 25° C. is 100.0 or more.

In addition, the present invention (9) provides the dielectric ceramiccomposition of any one of (1) to (8), wherein a change rate inelectrostatic capacity is within a range of −20.0% to 5.0% in atemperature range of −55° C. to 200° C.

In addition, the present invention (10) provides the dielectric ceramiccomposition of any one of (1) to (9), wherein a dielectric loss (tan δ)at 25° C. is 10.0% or less and a dielectric loss (tan δ) at 200° C. is10.0% or less.

In addition, the present invention (11) provides the dielectric ceramiccomposition of any one of (1) to (10), wherein an insulation resistancevalue at 200° C. is 40 MΩ or more and less than 100 MΩ.

In addition, the present invention (12) provides ceramic electroniccomponents, wherein a dielectric layer formed of the dielectric ceramiccomposition as described in any one of (1) to (11); and an electrodelayer comprising a base metal as a conductive component.

In addition, the present invention (13) provides the ceramic electroniccomponents of (12), wherein the base metal is at least one metalselected from nickel and copper.

In addition, the present invention (14) provides the ceramic electroniccomponents of (12) or (13), wherein a plurality of the dielectric layersand a plurality of the electrode layers are laminated.

Advantageous Effects of Invention

According to the present invention, the dielectric ceramic compositionthat can be fired under a reducing atmosphere, has a high relativedielectric constant, and, in the case where the dielectric ceramiccomposition is used as the dielectric layer of ceramic electroniccomponents such as a laminated ceramic capacitor, has a small change inelectrostatic capacity even under a high temperature condition of 150°C. to 200° C., a change rate in electrostatic capacity within a range of−50.0% to 50.0% (hereinafter, may be described as within ±50.0%) in atemperature range of −55° C. to 200° C., small dielectric losses at 25°C. and 200° C., and further can obtain a insulation resistance value at200° C. of 40 MΩ or more, and the ceramic electronic components in whichthe dielectric ceramic composition is used as the dielectric layer canbe provided.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a triangle diagram illustrating the suitable composition rangeof the dielectric ceramic composition according to the presentinvention.

FIG. 2 is a triangle diagram illustrating the further suitablecomposition range of the dielectric ceramic composition according to thepresent invention.

FIG. 3 is a SEM image (10,000 times) of Reference Sample 8.

FIG. 4 is a SEM image (10,000 times) of Reference Sample 15.

FIG. 5 is a SEM image (10,000 times) of Reference Sample 66.

FIG. 6 is a graph illustrating trends of the change rates of theelectrostatic capacity of Reference Samples 8, 15, and 66.

FIG. 7 is a graph illustrating trends of the change rates of theelectrostatic capacity of Reference Samples 15 and 78.

FIG. 8 is a sectional view schematically illustrating a ceramiccapacitor.

FIG. 9 is a chart illustrating the result of X-ray diffractionmeasurement of Reference Sample 15.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the present invention will be described with reference toembodiments illustrated in drawings. In the present invention, in thedescription of a numerical range “Δ to □”, the values of Δ and □ areincluded unless otherwise noted.

(Ceramic Capacitor 1)

The ceramic capacitor 1 illustrated in FIG. 8 includes a laminated body10 having a cuboid shape as a whole. The laminated body 10 isconstituted with a plurality of laminated dielectric layers 3 and aplurality of internal electrodes 2 a and 2 b formed along differentinterfaces of the dielectric layers 3. The internal electrodes 2 a and 2b are alternately arranged in the laminated body 10. Each of theinternal electrodes 2 a and 2 b is electrically connected to an externalelectrode 4 at different edges of the laminated body 10. On the externalelectrode 4, a first plated layer made of copper or a nickel-copperalloy, or the like may be formed and a second plated layer made ofsolder or tin, or the like may be further formed on the first platedlayer, if necessary.

As described above, the internal electrodes 2 a and 2 b are formed in astate where the internal electrodes overlap with each other in alaminated direction of the laminated body 10 and thus accumulateelectrical charge between the adjacent internal electrodes 2 a and 2 b.The electrical connection of the internal electrodes 2 a and 2 b and theexternal electrode 4 allows the charge to be taken out.

(Internal Electrodes 2 a and 2 b)

In the present invention, the base metal is used as a conductivecomponent for the internal electrodes 2 a and 2 b. As the base metal asthe conductive component, pure metals such as nickel, copper, andaluminum and, in addition to these metals, alloys, mixtures, orcomposites including these metal components may be used. As the basemetal as the conductive component, one metal selected from nickel andcopper is particularly preferable. The internal electrodes 2 a and 2 bmay include a conductive component in addition to the base metal and aninhibitor described below as long as the effects of the presentinvention are not impaired.

The internal electrodes 2 a and 2 b may be formed by any methods.Examples of the method include a method for forming the internalelectrodes using a conductive paste obtained by kneading a metal powderincluding the base metal with a binder component. In the case where theconductive paste is used, a method for forming the internal electrodesby a printing method such as screen printing is particularly preferableas the method for forming the internal electrodes 2 a and 2 b. In theconductive paste, as what is called inhibitor for controlling sinteringof the metal powder, a dielectric ceramic composition powder having thesame components as the components in the dielectric ceramic compositionaccording to the present invention described below may be included. Inaddition to the above method, the internal electrodes 2 a and 2 b mayalso be formed by known methods such as an ink-jet method, a vapordeposition method, and a plating method.

(Dielectric Layer 3)

The dielectric layer 3 is constituted of the dielectric ceramiccomposition according to the present invention described below, wherebythe change in the electrostatic capacity is small even in a widetemperature region, in particular, in a high temperature region ofaround 200° C., the change rate of the electrostatic capacity is within±50.0% in a temperature range of −55° C. to 200° C., and both dielectriclosses (tan δ) at 25° C. and 200° C. are 10.0% or less, while a highrelative dielectric constant is being maintained. In addition, thedielectric ceramic composition according to the present invention hasexcellent reduction resistance and thus is less likely to be reduced anddoes not transform to a semiconductor even in the case where the basemetal is used as the conductive component of the internal electrode andsimultaneous firing is performed under a reducing atmosphere.

(Dielectric Ceramic Composition)

The dielectric ceramic composition according to the first embodiment ofthe present invention includes the first component and the secondcomponent, in which

as a content ratio relative to a total number of moles of the firstcomponent when converted into following oxides, the first componentcomprises an oxide of Ca of 0.00 mol % to 35.85 mol % in terms of CaO,an oxide of Sr of 0.00 mol % to 47.12 mol % in terms of SrO, an oxide ofBa of 0.00 mol % to 51.22 mol % in terms of BaO, an oxide of Ti of 0.00mol % to 17.36 mol % in terms of TiO₂, an oxide of Zr of 0.00 mol % to17.36 mol % in terms of ZrO₂, an oxide of Sn of 0.00 mol % to 2.60 mol %in terms of SnO₂, an oxide of Nb of 0.00 mol % to 35.32 mol % in termsof Nb₂O₅, an oxide of Ta of 0.00 mol % to 35.32 mol % in terms of Ta₂O₅,and an oxide of V of 0.00 mol % to 2.65 mol % in terms of V₂O₅;

the first component comprises at least one oxide selected from the oxideof Ca, the oxide of Sr, and the oxide of Ba, at least one oxide selectedfrom the oxide of Ti and the oxide of Zr, and at least one oxideselected from the oxide of Nb and the oxide of Ta as essentialcomponents, and a total content ratio of the oxide of Ca in terms ofCaO, the oxide of Sr in terms of SrO, and the oxide of Ba in terms ofBaO is 48.72 mol % to 51.22 mol %, a total content ratio of the oxide ofTi in terms of TiO₂, the oxide of Zr in terms of ZrO₂, and the oxide ofSn in terms of SnO₂ is 15.97 mol % to 17.36 mol %, and a total contentratio of the oxide of Nb in terms of Nb₂O₅, the oxide of Ta in terms ofTa₂O₅, and the oxide of V in terms of V₂O₅ is 31.42 mol % to 35.31 mol %relative to the total number of moles of the first component whenconverted into the oxides; and

as a content ratio relative to a total mass of the first component whenconverted into the oxides, the second component comprises at least (a)an oxide of Mn of 0.005% by mass to 3.500% by mass in terms of MnO and(b) one or both of an oxide of Cu and an oxide of Ru.

The dielectric ceramic composition according to the first embodiment ofthe present invention includes the first component and the secondcomponent. In the dielectric ceramic composition according to the firstembodiment of the present invention, among oxides included in thedielectric ceramic composition, all oxides other than the oxidesincluded as the first component are included as the second component.

The first component of the dielectric ceramic composition according tothe first embodiment of the present invention comprises one or moreoxides selected from the oxide of Ca, the oxide of Sr, and the oxide ofBa, one or more oxides selected from the oxide of Ti and the oxide ofZr, and one or more oxides selected from the oxide of Nb and the oxideof Ta as essential components and one or more oxides selected from theoxide of Sn and the oxide of V as optional components.

In the dielectric ceramic composition according to the first embodimentof the present invention, as a content ratio relative to a total numberof moles of the first component when converted into the followingoxides, the content of each of the oxides existing in the firstcomponent is an oxide of Ca of 0.00 mol % to 35.85 mol % in terms ofCaO, an oxide of Sr of 0.00 mol % to 47.12 mol % in terms of SrO, anoxide of Ba of 0.00 mol % to 51.22 mol % in terms of BaO, an oxide of Tiof 0.00 mol % to 17.36 mol % in terms of TiO₂, an oxide of Zr of 0.00mol % to 17.36 mol % in terms of ZrO₂, an oxide of Sn of 0.00 mol % to2.60 mol % in terms of SnO₂, an oxide of Nb of 0.00 mol % to 35.32 mol %in terms of Nb₂O₅, an oxide of Ta of 0.00 mol % to 35.32 mol % in termsof Ta₂O₅, and an oxide of V of 0.00 mol % to 2.65 mol % in terms ofV₂O₅.

In the dielectric ceramic composition according to the first embodimentof the present invention, the total content ratio of the oxide of Ca interms of CaO, the oxide of Sr in terms of SrO, and the oxide of Ba interms of BaO relative to the total number of moles of the firstcomponent when converted into the above oxides is 48.72 mol % to 51.22mol % and preferably 49.37 mol % to 50.62 mol %.

In the dielectric ceramic composition according to the first embodimentof the present invention, the total content ratio of the oxide of Ti interms of TiO₂, the oxide of Zr in terms of ZrO₂, and the oxide of Sn interms of SnO₂ relative to the total number of moles of the firstcomponent when converted into the above oxides is 15.97 mol % to 17.36mol % and preferably 16.32 mol % to 17.01 mol %. In the case where thefirst component includes Sn, the content ratio of the oxide of Sn interms of SnO₂ relative to total number of moles of the oxide of Ti interms of TiO₂, the oxide of Zr in terms of ZrO₂, and the oxide of Sn interms of SnO₂ is 15.00 mol % or less.

In the dielectric ceramic composition according to the first embodimentof the present invention, the total content ratio of the oxide of Nb interms of Nb₂O₅, the oxide of Ta in terms of Ta₂O₅, and the oxide of V interms of V₂O₅ relative to the total number of moles of the firstcomponent when converted into the above oxides is 31.42 mol % to 35.31mol % and preferably 32.20 mol % to 34.43 mol %. In the case where thefirst component includes V, the content ratio of the oxide of V in termsof V₂O₅ relative to total number of moles of the oxide of Nb in terms ofNb₂O₅, the oxide of Ta in terms of Ta₂O₅, and the oxide of V in terms ofV₂O₅ is 7.50 mol % or less.

The dielectric ceramic composition according to the first embodiment ofthe present invention includes at least (a) component, that is, theoxide of Mn and (b) component, that is, the oxide of Cu, the oxide ofRu, or the oxide of Cu and the oxide of Ru as the second component. Inother words, the dielectric ceramic composition according to the firstembodiment of the present invention includes the oxide of Mn and one orboth of the oxide of Cu and the oxide of Ru as the essential secondcomponent.

In the dielectric ceramic composition according to the first embodimentof the present invention, the content of the oxide of Mn is 0.005% bymass to 3.500% by mass, preferably 0.005% by mass to 2.000% by mass, andparticularly preferably 0.010% by mass to 1.500% by mass in terms of MnOrelative to the total mass of the first component when converted intothe above oxides.

In the case where the dielectric ceramic composition according to thefirst embodiment of the present invention includes the oxide of Cu asthe second component, the content of the oxide of Cu is preferably0.010% by mass or more and less than 0.080% by mass, particularlypreferably 0.020% by mass or more and less than 0.080% by mass, and morepreferably 0.030% by mass or more and less than 0.080% by mass in termsof CuO relative to the total mass of the first component when convertedinto the above oxides.

In the case where the dielectric ceramic composition according to thefirst embodiment of the present invention includes the oxide of Ru asthe second component, the content of the oxide of Ru is 0.050% by massor more and less than 0.300% by mass, particularly preferably 0.100% bymass or more and less than 0.300% by mass, and more preferably 0.200% bymass or more and less than 0.300% by mass in terms of RuO₂ relative tothe total mass of the first component when converted into the aboveoxides.

The dielectric ceramic composition according to the first embodiment ofthe present invention includes the oxide of Mn having the above contentas the second component, whereby in the case where the dielectricceramic composition is used as a dielectric layer of the ceramicelectronic components such as a laminated ceramic capacitor, the changein the electrostatic capacity is small even in a high temperaturecondition of 150° C. to 200° C., the change rate of the electrostaticcapacity is within ±50.0% in a temperature range of −55° C. to 200° C.,and the dielectric losses (tan δ) at 25° C. and 200° C. are small.

The dielectric ceramic composition according to the first embodiment ofthe present invention, in which the content of the first component isdetermined to be the above content and the oxide of Mn is included inthe above content as the second component, exhibits the effects in whichthe change in the electrostatic capacity is small in a high temperaturecondition of 150° C. to 200° C., the change rate of the electrostaticcapacity is within ±50.0% in a temperature range of −55° C. to 200° C.,and the dielectric losses (tan δ) at 25° C. and 200° C. are small. Inaddition, the dielectric ceramic composition according to the firstembodiment of the present invention, in which one or both of the oxideof Cu and the oxide of Ru are included as the second component, canprovide the high insulation resistance value without significantlyaffecting the effects caused by determining the content of the firstcomponent to be the above content and including the oxide of Mn in theabove content as the second component, that is, the effects in which thechange in the electrostatic capacity is small in a high temperaturecondition of 150° C. to 200° C., the change rate of the electrostaticcapacity is within ±50.0% in a temperature range of −55° C. to 200° C.,and the dielectric losses at 25° C. and 200° C. are small.

The dielectric ceramic composition according to the first embodiment ofthe present invention includes (a) the oxide of Mn and (b) any one orboth of the oxide of Cu and the oxide of Ru and, in addition to theabove components, the oxides (hereinafter, also described as a (c)component) other than the (a) component and the (b) component may beoptionally included as the second component. The second component isadded to the dielectric ceramic composition according to the presentinvention for the purpose of improving the reduction resistance andother properties. The ratio of total mass of the second component otherthan the (b) component in terms of the oxides (that is, the total massof the (a) component and the (c) component) is preferably 10.000% bymass or less and particularly preferably 0.100% by mass to 5.500% bymass relative to the total mass of the first component when convertedinto the above oxides.

The optional component of the second component included in thedielectric ceramic composition according to the first embodiment of thepresent invention is preferably the oxides of D (D is at least oneelement selected from Li, Mg, Si, Cr, Al, Fe, Co, Ni, Zn, Ga, Ge, In, W,Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu)and the oxide of Mg, the oxide of Si, and the oxide of Y areparticularly preferable.

The mass of the oxide of D is a converted value of Li in terms of Li₂O,Mg in terms of MgO, Si in terms of SiO₂, Cr in terms of Cr₂O₃, Al interms of Al₂O₃, Fe in terms of Fe₂O₃, Co in terms of CoO, Ni in terms ofNiO, Zn in terms of ZnO, Ga in terms of Ga₂O₃, Ge in terms of GeO₂, Inin terms of In₂O₃, Win terms of WO₃, Mo in terms of MoO₃, Yin terms ofY₂O₃, Hf in terms of HfO₂, La in terms of La₂O₃, Ce in terms of CeO₂, Prin terms of Pr₆O₁₁, Nd in terms of Nd₂O₃, Sm in terms of Sm₂O₃, Eu interms of Eu₂O₃, Gd in terms of Gd₂O₃, Tb in terms of Tb₄O₇, Dy in termsof Dy₂O₃, Ho in terms of Ho₂O₃, Er in terms of Er₂O₃, Tm in terms ofTm₂O₃, Yb in terms of Yb₂O₃, or Lu in terms of Lu₂O₃.

The dielectric ceramic composition according to the first embodiment ofthe present invention preferably exhibits existence of the tungstenbronze type crystal phase when crystal structure analysis such as X-raydiffraction is performed. The average grain size of the dielectricceramic composition according to the first embodiment of the presentinvention is preferably 5 or less and particularly preferably 3 μm orless.

The dielectric ceramic composition according to the second embodiment ofthe present invention includes the first component and the secondcomponent, in which

as the first component, a compound represented by a following generalformula (1):

A_(a)M¹ _(b)M² _(c)O_(d)  (1)

(in the formula (1), A is represented by a general formula (2):

Ba_(1-x-y)Sr_(x)Ca_(y)  (2)

(in the formula (2), 0≤x≤0.920 and 0≤y≤0.700); M¹ is at least oneelement selected from Ti, Zr, and Sn; M² is at least one elementselected from Nb, Ta, and V; and 5.70≤a≤6.30, 1.90≤b≤2.10, 7.20≤c≤8.80,and 27.45≤d≤32.50) is included (with the proviso that, when Sn isincluded, the content ratio of the oxide of Sn in terms of SnO₂ relativeto the total number of moles of the oxide of Ti in terms of TiO₂, theoxide of Zr in terms of ZrO₂, and the oxide of Sn in terms of SnO₂ is15.00 mol % or less and when V is included, the content ratio of theoxide of V in terms of V₂O₅ relative to the total number of moles of theoxide of Nb in terms of Nb₂O₅, the oxide of Ta in terms of Ta₂O₅, andthe oxide of V in terms of V₂O₅ is 7.50 mol % or less), and

as a content ratio relative to a total mass of the first component whenthe first component is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂,Nb₂O₅, Ta₂O₅, and V₂O₅, the second component comprises at least (a) anoxide of Mn of 0.005% by mass to 3.500% by mass in terms of MnO and (b)one or both of an oxide of Cu and an oxide of Ru.

The dielectric ceramic composition according to the second embodiment ofthe present invention includes the first component and the secondcomponent. In the dielectric ceramic composition according to the secondembodiment of the present invention, among oxides included in thedielectric ceramic composition, all oxides other than the oxidesincluded as the first component are included as the second component.

In the dielectric ceramic composition according to the second embodimentof the present invention, the first component is a compound representedby the following general formula (1):

A_(a)M¹ _(b)M² _(c)O_(d)  (1).

In the general formula (1), A is represented by the general formula (2):

Ba_(1-x-y)Sr_(x)Ca_(y)  (2)

(in the formula (2), 0≤x≤0.920 and 0≤y≤0.700). In other words, A may beBa alone, a combination of any of two of Ca, Sr, and Ba (Ca and Sr, Caand Ba, or Sr and Ba), or a combination of Ca, Sr, and Ba.

In the general formula (1), M¹ is at least one element selected from Ti,Zr, and Sn. Here, one or more elements selected from Ti and Zr areessential as M¹. More specifically, M¹ is Ti alone, Zr alone, acombination of Ti and Sn, a combination of Zr and Sn, a combination ofTi and Zr, or a combination of Ti, Zr, and Sn.

In the general formula (1), M² is at least one element selected from Nb,Ta, and V. Here, one or more elements selected from Nb and Ta areessential as M². More specifically, M² is Nb alone, Ta alone, acombination of Nb and V, a combination of Ta and V, a combination of Nband Ta, or a combination of Nb, Ta, and V.

In the general formula (1), a is in the range of 5.70≤a≤6.30, b is inthe range of 1.90≤b≤2.10, c is in the range of 7.20≤c≤8.80, and d is inthe range of 27.45≤d≤32.50.

In the case where the dielectric ceramic composition according to thesecond embodiment of the present invention includes Sn, the contentratio of the oxide of Sn in terms of SnO₂ relative to total number ofmoles of the oxide of Ti in terms of TiO₂, the oxide of Zr in terms ofZrO₂, and the oxide of Sn in terms of SnO₂ is 15.00 mol % or less. Inthe case where the dielectric ceramic composition according to thesecond embodiment of the present invention includes V, the content ratioof the oxide of V in terms of V₂O₅ relative to total number of moles ofthe oxide of Nb in terms of Nb₂O₅, the oxide of Ta in terms of Ta₂O₅,and the oxide of V in terms of V₂O₅ is 7.50 mol % or less.

The dielectric ceramic composition according to the second embodiment ofthe present invention includes at least the (a) component, that is, theoxide of Mn and the (b) component, that is, the oxide of Cu, the oxideof Ru, or the oxide of Cu and the oxide of Ru as the second component.In other words, the dielectric ceramic composition according to thesecond embodiment of the present invention includes the oxide of Mn andone or both of the oxide of Cu and the oxide of Ru as the essentialsecond component.

In the dielectric ceramic composition according to the second embodimentof the present invention, the content of the oxide of Mn is 0.005% bymass to 3.500% by mass, preferably 0.005% by mass to 2.000% by mass, andparticularly preferably 0.010% by mass to 1.500% by mass in terms of MnOrelative to the total mass of the first component when the firstcomponent is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅,Ta₂O₅, and V₂O₅.

In the case where the dielectric ceramic composition according to thesecond embodiment of the present invention includes the oxide of Cu asthe second component, the content of the oxide of Cu is preferably0.010% by mass or more and less than 0.080% by mass, particularlypreferably 0.020% by mass or more and less than 0.080% by mass, and morepreferably 0.030% by mass or more and less than 0.080% by mass in termsof CuO relative to the total mass of the first component when the firstcomponent is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅,Ta₂O₅, and V₂O₅.

In the case where the dielectric ceramic composition according to thesecond embodiment of the present invention includes the oxide of Ru asthe second component, the content of the oxide of Ru is preferably0.050% by mass or more and less than 0.300% by mass, particularlypreferably 0.100% by mass or more and less than 0.300% by mass, and morepreferably 0.200% by mass or more and less than 0.300% by mass in termsof RuO₂ relative to the total mass of the first component when the firstcomponent is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅,Ta₂O₅, and V₂O₅.

The dielectric ceramic composition according to the second embodiment ofthe present invention includes the (a) component, that is, the oxide ofMn having the above content as the second component, whereby in the casewhere the dielectric ceramic composition is used as a dielectric layerof the ceramic electronic components such as a laminated ceramiccapacitor, the change in the electrostatic capacity is small even in ahigh temperature condition of 150° C. to 200° C., the change rate of theelectrostatic capacity is within ±50.0% in a temperature range of −55°C. to 200° C., and the dielectric losses (tan δ) at 25° C. and 200° C.are small.

The dielectric ceramic composition according to the second embodiment ofthe present invention, in which the content of the first component isdetermined to be the above content and the oxide of Mn is included inthe above content as the second component, exhibits the effects in whichthe change in the electrostatic capacity is small in a high temperaturecondition of 150° C. to 200° C., the change rate of the electrostaticcapacity is within ±50.0% in a temperature range of −55° C. to 200° C.,and the dielectric losses (tan δ) at 25° C. and 200° C. are small. Inaddition, the dielectric ceramic composition according to the secondembodiment of the present invention, in which one or both of the oxideof Cu and the oxide of Ru are included as the second component, canprovide the high insulation resistance value without significantlyaffecting the effects caused by determining the content of the firstcomponent to be the above content and including the oxide of Mn in theabove content as the second component, that is, the effects in which thechange in the electrostatic capacity is small in a high temperaturecondition of 150° C. to 200° C., the change rate of the electrostaticcapacity is within ±50.0% in a temperature range of −55° C. to 200° C.,and the dielectric losses at 25° C. and 200° C. are small.

The dielectric ceramic composition according to the second embodiment ofthe present invention includes (a) the oxide of Mn and (b) any one orboth of the oxide of Cu and the oxide of Ru and, in addition to theabove components, the oxides (hereinafter, also described as a (c)component) other than the oxides of the (a) component and the (b)component may be optionally included as the second component. The secondcomponent is added to the dielectric ceramic composition according tothe present invention for the purpose of improving the reductionresistance and other properties. The total mass of the second componentother than the (b) component in terms of the oxides (that is, the totalmass of the (a) component and the (c) component) is preferably 10.000%by mass or less and particularly preferably 0.100% by mass to 5.500% bymass relative to the total mass of the first component when the firstcomponent is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅,Ta₂O₅, and V₂O₅.

The optional component of the second component included in thedielectric ceramic composition according to the second embodiment of thepresent invention is preferably the oxides of D (D is at least oneelement selected from Li, Mg, Si, Cr, Al, Fe, Co, Ni, Zn, Ga, Ge, In, W,Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu)and the oxide of Mg, the oxide of Si, and the oxide of Y areparticularly preferable.

The mass of the oxide of D is a converted value of Li in terms of Li₂O,Mg in terms of MgO, Si in terms of SiO₂, Cr in terms of Cr₂O₃, Al interms of Al₂O₃, Fe in terms of Fe₂O₃, Co in terms of CoO, Ni in terms ofNiO, Zn in terms of ZnO, Ga in terms of Ga₂O₃, Ge in terms of GeO₂, Inin terms of In₂O₃, Win terms of WO₃, Mo in terms of MoO₃, Yin terms ofY₂O₃, Hf in terms of HfO₂, La in terms of La₂O₃, Ce in terms of CeO₂, Prin terms of Pr₆O₁₁, Nd in terms of Nd₂O₃, Sm in terms of Sm₂O₃, Eu interms of Eu₂O₃, Gd in terms of Gd₂O₃, Tb in terms of Tb₄O₇, Dy in termsof Dy₂O₃, Ho in terms of Ho₂O₃, Er in terms of Er₂O₃, Tm in terms ofTm₂O₃, Yb in terms of Yb₂O₃, or Lu in terms of Lu₂O₃.

The dielectric ceramic composition according to the second embodiment ofthe present invention exhibits existence of the tungsten bronze typecrystal phase when crystal structure analysis such as X-ray diffractionis performed. The average grain size thereof is preferably 5 or less andparticularly preferably 3 μm or less.

The dielectric ceramic composition according to the third embodiment ofthe present invention includes the first component and the secondcomponent, in which

a compound represented by a following general formula (3):

α·Ca_(η1)M³ _(θ1)M⁴ _(ϕ1)-β·Sr_(η2)M³ _(θ2)M⁴ _(ϕ2)O_(ω2-γ)·Ba_(η3)M³_(θ3)M⁴ _(ϕ3)O_(ω3)  (3)

(in the formula (3), η1, η2, and η3 are each independently values withina range of 5.70 to 6.30; θ1, θ2, and θ3 are each independently valueswithin a range of 0.95 to 1.05; ϕ1, ϕ2, and ϕ3 are each independentlyvalues within a range of 0.90 to 1.10; ω1, ω2, and ω3 are eachindependently values within a range of 27.45 to 32.50; M³ is representedby a general formula (4):

Ti_(2-ρ-σ)Zr_(ρ)Sn_(σ)  (4)

(in the formula (4), 0≤p≤2.0 and 0≤σ≤0.3); M⁴ is represented by ageneral formula (5):

Nb_(8-π-ψ)Ta_(π)V_(ψ)  (5)

(in the formula (5), 0≤π≤8.0 and 0≤ψ≤0.6); and α, β, and γ satisfyα+β+γ=1.00), and when an arbitrary point in a ternary compositiondiagram is represented as (α, β, γ), the compound existing within arange surrounded by line segments linking a point A=(0.05, 0.95, 0.00),a point B=(0.70, 0.30, 0.00), a point C=(0.70, 0.00, 0.30), a pointD=(0.00, 0.00, 1.00), and a point E=(0.00, 0.90, 0.10) is included asthe first component; and

as a content ratio relative to a total mass of the first component whenthe first component is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂,Nb₂O₅, Ta₂O₅, and V₂O₅, the second component comprises at least (a) anoxide of Mn of 0.005% by mass to 3.500% by mass in terms of MnO and (b)one or both of an oxide of Cu and an oxide of Ru.

The dielectric ceramic composition according to the third embodiment ofthe present invention includes the first component and the secondcomponent. In the dielectric ceramic composition according to the thirdembodiment of the present invention, among oxides included in thedielectric ceramic composition, all oxides other than the oxidesincluded as the first component are included as the second component.

The first component of the dielectric ceramic composition according tothe third embodiment of the present invention is a compound existingwithin the range surrounded by line segments linking a point A=(0.05,0.95, 0.00), a point B=(0.70, 0.30, 0.00), a point C=(0.70, 0.00, 0.30),a point D=(0.00, 0.00, 1.00), and a point E=(0.00, 0.90, 0.10)(hereinafter, may also be described as a compound existing within therange surrounded by line segments linking the point A, the point B, thepoint C, the point D, and the point E on the ternary composition diagramillustrated in FIG. 1) when a point on the ternary composition diagramof Ca_(η1)M³ _(θ1)M⁴ _(ϕ1)O_(ω1)-Sr_(η2)M³ _(θ2)M⁴ _(ϕ2)O_(ω2)-Ba_(η3)M³_(θ3)M⁴ _(ϕ3)O_(ω3) illustrated in FIG. 1 is represented by (α, β, γ)(here, α, β, and γ satisfy α+β+γ=1.00). The first component having thecomposition existing within the above range allows the relativedielectric constant at 25° C. to be 100.0 or more and thus exhibitsferroelectricity.

The first component of the dielectric ceramic composition according tothe third embodiment of the present invention is preferably a compoundexisting within the range surrounded by line segments linking a pointA′=(0.05, 0.95, 0.00), a point B′=(0.60, 0.40, 0.00), a point C′=(0.70,0.20, 0.10), a point D′=(0.70, 0.10, 0.20), a point E′=(0.55, 0.00,0.45), a point F′=(0.40, 0.00, 0.60), a point G′=(0.10, 0.10, 0.80), apoint H′=(0.00, 0.00, 1.00), a point I′=(0.00, 0.40, 0.60) a pointJ′=(0.20, 0.40, 0.40), a point K′=(0.00, 0.70, 0.30), and a pointL′=(0.00, 0.90, 0.10) (hereinafter, may also be described as a compoundexisting within the range surrounded by line segments linking the pointA′, the point B′, the point C′, the point D′, the point E′, the pointF′, the point G′, the point H′, the point I′, the point J′, the pointK′, and the point L′ on the ternary composition diagram illustrated inFIG. 2) on the ternary composition diagram of Ca_(η1)M³ _(θ1)M⁴_(ϕ1)O_(ω1)-Sr_(η2)M³ _(θ2)M⁴ _(ϕ2)O_(ω2)-Ba_(η3)M³ _(θ3)M⁴ _(ϕ3)O_(ω3)illustrated in FIG. 2. The first component having the compositionexisting within the above range is likely to provide the relativedielectric constant at 25° C. of 200 or more and thus exhibitsferroelectricity. The ternary composition diagram of “Ca_(η1)M³ _(θ1)M⁴_(ϕ1)O_(ω1)-Sr_(η2)M³ _(θ2)M⁴ _(ϕ2)O_(ω2)-Ba_(η3)M³ _(θ3)M⁴ _(ϕ3)O_(ω3)”illustrated in FIG. 2 is the same diagram as the ternary compositiondiagram of “Ca_(η1)M³ _(θ1)M⁴ _(ϕ1)O_(ω1)-Sr_(η2)M³ _(θ2)M⁴_(ϕ2)O_(ω2)-Ba_(η3)M³ _(θ3)M⁴ _(ϕ3)O_(ω3)” illustrated in FIG. 1.

Here, in the ternary composition diagram of “Ca_(η1)M³ _(θ1)M⁴_(ϕ1)O_(ω1)-Sr_(η2)M³ _(θ2)M⁴ _(ϕ2)O_(ω2)-Ba_(η3)M³ _(θ3)M⁴ _(ϕ3)O_(ω3)”according to the dielectric ceramic composition of the third embodimentof the present invention, η1, η2, and η3 are each independently valueswithin the range of 5.70 to 6.30. θ1, θ2, and θ3 are each independentlyvalues within the range of 0.95 to 1.05. ω1, ω2, and ω3 are eachindependently values within the range of 0.90 to 1.10. ω1, ω2, and ω3are each independently values within the range of 27.45 to 32.50. M³ isa general formula (4):

Ti_(2-ρ-σ)Zr_(ρ)Sn_(σ)  (4)

(in the formula (4), 0≤ρ≤2.0 and 0≤σ≤0.3). M⁴ is a general formula (5):

Nb_(8-π-ψ)Ta_(π)V_(ψ)  (5)

(in the formula (5), 0≤π≤8.0 and 0≤ψ≤0.6).

The dielectric ceramic composition according to the third embodiment ofthe present invention includes at least the (a) component, that is, theoxide of Mn and the (b) component, that is, the oxide of Cu, the oxideof Ru, or the oxide of Cu and the oxide of Ru as the second component.In other words, the dielectric ceramic composition according to thethird embodiment of the present invention includes the oxide of Mn andone or both of the oxide of Cu and the oxide of Ru as the essentialsecond component.

In the dielectric ceramic composition according to the third embodimentof the present invention, the content of the oxide of Mn is 0.005% bymass to 3.500% by mass, preferably 0.005% by mass to 2.000% by mass, andparticularly preferably 0.010% by mass to 1.500% by mass in terms of MnOrelative to the total mass of the first component when the firstcomponent is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅,Ta₂O₅, and V₂O₅.

In the case where the dielectric ceramic composition according to thethird embodiment of the present invention includes the oxide of Cu asthe second component, the content of the oxide of Cu is preferably0.010% by mass or more and less than 0.080% by mass, particularlypreferably 0.020% by mass or more and less than 0.080% by mass, and morepreferably 0.030% by mass or more and less than 0.080% by mass in termsof CuO relative to the total mass of the first component when the firstcomponent is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅,Ta₂O₅, and V₂O₅.

In the case where the dielectric ceramic composition according to thethird embodiment of the present invention includes the oxide of Ru asthe second component, the content of the oxide of Ru is preferably0.050% by mass or more and less than 0.300% by mass, particularlypreferably 0.100% by mass or more and less than 0.300% by mass, and morepreferably 0.200% by mass or more and less than 0.300% by mass in termsof RuO₂ relative to the total mass of the first component when the firstcomponent is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅,Ta₂O₅, and V₂O₅.

The dielectric ceramic composition according to the third embodiment ofthe present invention includes the (a) component, that is, the oxide ofMn having the above content as the second component, whereby in the casewhere the dielectric ceramic composition is used as a dielectric layerof the ceramic electronic components such as a laminated ceramiccapacitor, the change in the electrostatic capacity is small even in ahigh temperature condition of 150° C. to 200° C., the change rate of theelectrostatic capacity is within ±50.0% in a temperature range of −55°C. to 200° C., and the dielectric losses (tan δ) at 25° C. and 200° C.are small.

The dielectric ceramic composition according to the third embodiment ofthe present invention, in which the content of the first component isdetermined to be the above content and the oxide of Mn is included inthe above content as the second component, exhibits the effects in whichthe change in the electrostatic capacity is small in a high temperaturecondition of 150° C. to 200° C., the change rate of the electrostaticcapacity is within ±50.0% in a temperature range of −55° C. to 200° C.,and the dielectric losses (tan δ) at 25° C. and 200° C. are small. Inaddition, the dielectric ceramic composition according to the thirdembodiment of the present invention, in which one or both of the oxideof Cu and the oxide of Ru are included as the second component, canprovide the high insulation resistance value under a high temperatureenvironment without significantly affecting the effects caused bydetermining the content of the first component to be the above contentand including the oxide of Mn in the above content as the secondcomponent, that is, the effects in which the change in the electrostaticcapacity is small in a high temperature condition of 150° C. to 200° C.,the change rate of the electrostatic capacity is within ±50.0% in atemperature range of −55° C. to 200° C., and the dielectric losses at25° C. and 200° C. are small.

The dielectric ceramic composition according to the third embodiment ofthe present invention includes (a) the oxide of Mn and (b) any one orboth of the oxide of Cu and the oxide of Ru and, in addition to theabove components, the oxides (hereinafter, also described as a (c)component) other than the (a) component and the (b) component may beoptionally included as the second component. The second component isadded to the dielectric ceramic composition according to the presentinvention for the purpose of improving the reduction resistance andother properties. The total mass of the second component other than the(b) component in terms of the oxides (that is, the total mass of the (a)component and the (c) component) is preferably 10.000% by mass or lessand particularly preferably 0.100% by mass to 5.500% by mass relative tothe total mass of the first component when the first component isconverted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅, Ta₂O₅, and V₂O₅.

The optional component of the second component included in thedielectric ceramic composition according to the third embodiment of thepresent invention is preferably the oxides of D (D is at least oneelement selected from Li, Mg, Si, Cr, Al, Fe, Co, Ni, Zn, Ga, Ge, In, W,Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu)and the oxide of Mg, the oxide of Si, and the oxide of Y areparticularly preferable.

The mass of the oxide of D is a converted value of Li in terms of Li₂O,Mg in terms of MgO, Si in terms of SiO₂, Cr in terms of Cr₂O₃, Al interms of Al₂O₃, Fe in terms of Fe₂O₃, Co in terms of CoO, Ni in terms ofNiO, Zn in terms of ZnO, Ga in terms of Ga₂O₃, Ge in terms of GeO₂, Inin terms of In₂O₃, Win terms of WO₃, Mo in terms of MoO₃, Yin terms ofY₂O₃, Hf in terms of HfO₂, La in terms of La₂O₃, Ce in terms of CeO₂, Prin terms of Pr₆O₁₁, Nd in terms of Nd₂O₃, Sm in terms of Sm₂O₃, Eu interms of Eu₂O₃, Gd in terms of Gd₂O₃, Tb in terms of Tb₄O₇, Dy in termsof Dy₂O₃, Ho in terms of Ho₂O₃, Er in terms of Er₂O₃, Tm in terms ofTm₂O₃, Yb in terms of Yb₂O₃, or Lu in terms of Lu₂O₃.

The dielectric ceramic composition according to the third embodiment ofthe present invention exhibits existence of the tungsten bronze typecrystal phase when crystal structure analysis such as X-ray diffractionis performed. The average grain size thereof is preferably 5 μm or lessand particularly preferably 3 μm or less.

In the dielectric ceramic composition according to the first embodimentof the present invention, the dielectric ceramic composition accordingto the second embodiment of the present invention, and the dielectricceramic composition according to the third embodiment of the presentinvention, as the relative dielectric constant at 25° C. becomes higher,the dielectric ceramic composition becomes more preferable. The relativedielectric constant is 100.0 or more and preferably 200.0 or more, anddepending on the composition, preferably 300.0 or more, furtherpreferably 400.0 or more, and further preferably 500.0 or more.

In the dielectric ceramic composition according to the first embodimentof the present invention, the dielectric ceramic composition accordingto the second embodiment of the present invention, and the dielectricceramic composition according to the third embodiment of the presentinvention, the change rate of the electrostatic capacity is within±50.0% and preferably within the range of −33.0% to 22.0% in thetemperature range of −55° C. to 200° C. In the present invention, thechange rate of the electrostatic capacity refers to a value obtained bythe method described below.

In the dielectric ceramic composition according to the first embodimentof the present invention, the dielectric ceramic composition accordingto the second embodiment of the present invention, and the dielectricceramic composition according to the third embodiment of the presentinvention, the dielectric loss (tan δ) at 25° C. is 10.0% or less andthe dielectric loss (tan δ) at 200° C. is 10.0% or less, which providesexcellent high-frequency properties.

In the dielectric ceramic composition according to the first embodimentof the present invention, the dielectric ceramic composition accordingto the second embodiment of the present invention, and the dielectricceramic composition according to the third embodiment of the presentinvention, the insulation resistance value at 200° C. is preferably 40MΩ or more, and in particular, the insulation resistance value at 200°C. is preferably 40 MΩ or more and less than 100 MΩ.

In the dielectric ceramic composition according to the first embodimentof the present invention, the dielectric ceramic composition accordingto the second embodiment of the present invention, and the dielectricceramic composition according to the third embodiment of the presentinvention, change in electrostatic capacity is small even under a hightemperature condition of 150° C. to 200° C. and the change rate of theelectrostatic capacity is within a range of −50.0% to 50.0%, preferablywithin a range of −33.0% to 22.0%, and particularly preferably −20.0% to5.0% in a temperature range of −55° C. to 200° C. The dielectric ceramiccomposition according to the present invention is suitable for theelectronic components for which the high insulation resistance value isrequired in addition to the small dielectric losses at 25° C. to 200° C.

The dielectric ceramic composition according to the first embodiment ofthe present invention, the dielectric ceramic composition according tothe second embodiment of the present invention, and the dielectricceramic composition according to the third embodiment of the presentinvention can be fired under a reducing atmosphere.

(External Electrode 4)

The external electrode 4 is formed by applying a conductive paste forthe external electrode to the edge after the laminated body 10 isco-fired and firing the applied paste. The present invention, however,is not limited thereto. The external electrode 4 may also be formed byheat treatment using a paste including a thermosetting resin or athermoplastic resin. The conductive component used for the conductivepaste for the external electrode is not particularly limited. Forexample, pure metals such as nickel, copper, silver, palladium,platinum, and gold and, in addition to these metals, alloys, mixtures,or composites including these metal components may be used. As otheradditives, glass frit may be added to the conductive paste, ifnecessary. The external electrode 4 may also be co-fired together withthe laminated body 10.

(Method for Producing Ceramic Capacitor 1)

The ceramic capacitor 1 is produced by known methods except using thedielectric ceramic composition according to the first embodiment of thepresent invention, the dielectric ceramic composition according to thesecond embodiment of the present invention, or the dielectric ceramiccomposition according to the third embodiment of the present invention.Hereinafter, one example will be described.

First, starting materials for forming the dielectric layer 3 areprovided. Examples of the starting materials include oxides such as CaO,SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅, Ta₂O₅, and V₂O₅, and carbonates andnitrates, or the like, which generate these oxides by firing.

These starting materials are weighed so as to be a target compositionand mixed. The obtained mixture was calcinated at a temperature of about700° C. to about 900° C. for about 3 hours to about 6 hours in the air.Subsequently, the obtained product is finely pulverized and the obtaineddielectric raw material is used as the raw material for the firstcomponent.

In addition, a Mn compound such as MnO and MnCO₃ as a Mn source, a Cucompound such as CuO, Cu₂O, Cu(NO₃)₂, Cu(OH)₂, and CuCO₃ as a Cu sourcein the case where the oxide of Cu is included as the second component, aRu compound such as RuO₂, RuO₄, Ru₃(CO)₁₂ as a Ru source in the casewhere the oxide of Ru is included as the second component, and compoundsincluding Li, Mg, Si, Cr, Al, Fe, Co, Ni, Zn, Ga, Ge, In, W, Mo, Y, Hf,La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or the like, tobe added, if necessary, are provided as a raw material for the secondcomponent.

Subsequently, the raw materials for the first component and the rawmaterials for the second component are kneaded and dispersed in anappropriate binder component to prepare a dielectric paste or adielectric slurry. In the dielectric paste or the dielectric slurry,additives such as a plasticizer may be included, if necessary.

Subsequently, the obtained dielectric paste or dielectric slurry isformed into a sheet-like shape. Subsequently, a conductor pattern isformed using the conductive paste for the internal electrode describedabove on the surface of the obtained green sheet. This operation isrepeated predetermined times to stack the sheets, which are pressed tobe consolidated to yield an unfired laminated body (hereinafter, thislaminated body is referred to as a green chip).

Subsequently, debinding is performed on the green chip, if necessary.The conditions for the debinding are not particularly limited. Examplesof the conditions include heat treatment at a retention temperature of180° C. to 400° C. for 1 hour to 3 hours.

Subsequently, the green chip is fired at about 1,150° C. to about 1,350°C. under a reducing atmosphere to provide a fired laminated body 10(hereinafter, referred to as a sintered compact 10).

Thereafter, the sintered compact 10 is subjected to re-oxidationtreatment (hereinafter, referred to as annealing), if necessary. Theannealing conditions may be known conditions widely used in the art. Forexample, oxygen partial pressure at the time of annealing is preferablyset to higher oxygen partial pressure than the oxygen partial pressureat the time of firing and the holding temperature is preferably set to1,100° C. or less.

The sintered compact 10 obtained as described above is subjected to endpolishing and thereafter the conductive paste for the external electrodeis applied. The applied paste is fired to form the external electrode 4.The above-described plating layer is formed on the surface of theexternal electrode 4, if necessary.

Thus obtained ceramic capacitor 1 is implemented on, for example, aprinted circuit board by, for example, soldering and used for variouselectronic devices and the like.

As described above, the embodiments of the present invention havedescribed. The present invention, however, is not limited to theabove-described embodiments at all and is used for various applicationswithout departing from the scope of the present invention.

For example, although the ceramic capacitor has been described in theabove description, the present invention is applicable for other ceramicelectronic components such as an inductor and an actuator.

Hereinafter, the present invention will be described with reference tospecific experimental examples. However, the present invention in notlimited thereto. The compositions of the dielectric ceramic compositiondescribed below is presumed by the raw material composition (feedcomposition) and crystal structure analysis. The same applies in thepresent specification.

EXAMPLE

First, confirmation tests for determination of the content of the firstcomponent and the effect of addition of the oxide of Mn were conducted(Reference Samples 1 to 90 and Reference Samples 91 to 107).

Reference Example 1

(1) Preparation of Reference Samples 1 to 90 of Dielectric CeramicComposition

As the starting materials of the first component, each powder of CaCO₃,SrCO₃, BaCO₃, TiO₂, ZrO₂, SnO₂, Nb₂O₅, Ta₂O₅, and V₂O₅ was weighed sothat the ratio of each powder in terms of the oxide was as listed inTable 1, Table 3, and Table 5 and the resultant mixture was wet-blendedfor 20 hours with pure water using a ball mill.

Subsequently, each of the blends was dried at 100° C. and thereaftercalcinated at 750° C. to 900° C. for 3 hours in the air. The obtainedproduct was similarly finely pulverized again with the ball mill toprepare the dielectric raw material for the first component.

As the second component, a mixture made by weighing and mixing 18.2 mgof MnCO₃, 32 mg of MgO, 58.6 mg of SiO₂, and 89.5 mg Y₂O₃ was providedand the mixture was used as the raw material for second component. Here,in Reference Sample 43, only three components of MnCO₃, MgO, and Y₂O₃excluding SiO₂ were used as the raw materials for the second component.In Reference Sample 44, only three components of MnCO₃, SiO₂, and Y₂O₃excluding MgO were used as the raw materials for the second component.In Reference Sample 45, only three components of MnCO₃, MgO, and SiO₂excluding Y₂O₃ were used. In Reference Samples 78 and 79, only threecomponents of MgO, SiO₂, and Y₂O₃ excluding MnCO₃ were used. Of the rawmaterial for the second component, the amount of MnCO₃ was changed to0.404 mg in Reference Sample 41, the amount of MnCO₃ was changed to0.198 g in Reference Sample 42, and the amount of MnCO₃ was changed to2.055 g in Reference Sample 80.

A poly(vinyl alcohol) aqueous solution was prepared by chargingion-exchanged water and polyvinyl alcohol in a container so that thepolyvinyl alcohol concentration was 6% by mass and mixing the resultantmixture at 90° C. for 1 hour.

Then, 25 g of each of the dielectric raw materials for the firstcomponent and the raw material for the second component having theabove-described amount were mixed. The polyvinyl alcohol aqueoussolution was added to the raw material mixture so that the concentrationof the polyvinyl alcohol aqueous solution was 10% by mass relative tothe resultant mixture and the resultant product was mixed and granulatedin a mortar to prepare a granulated powder.

Furthermore, the obtained granulated powder was charged in a mold havinga diameter of 14.0 mm and press-molded at a pressure of 1 ton/cm² toprovide a disk-shaped green compact.

Subsequently, the obtained green compact was fired in a reducingatmosphere to prepare a sintered compact. In this firing, thetemperature increasing rate, the holding temperature, and the holdingtime were set to 300° C./h, 1,150° C. to 1,300° C., and two hours,respectively. As an atmosphere gas, moistened hydrogen/nitrogen mixturegas (hydrogen concentration 0.5%) was used and a wetter (wettertemperature 35° C.) was used for the moistening.

Subsequently, with respect to the obtained sintered compact, In—Gaelectrodes having a diameter of 8 mm were applied to the two mainsurfaces of the sintered compact to provide a disk-shaped ceramiccapacitor of respective Reference Samples 1 to 90.

(2) Analysis of Reference Samples 1 to 90 of Dielectric CeramicComposition

With respect to the disk-shaped ceramic capacitors of correspondingReference Samples 1 to 90 obtained as described above, each of the grainsize, the crystal phase, the relative dielectric constant, the changerate of the electrostatic capacity, and the dielectric loss (tan δ) wasanalyzed. The results are listed in Table 2, Table 4, and Table 6.

<Grain Size>

The surface of each of the capacitor was observed using a scanningelectron microscope (SEM). The average value of equivalent circlediameters determined from grain boundaries of randomly selected 20crystal grains was determined to be the grain size. FIG. 3, FIG. 4, andFIG. 5 are SEM images of Reference Samples 8, 15, and 66, respectively.

<Crystal Phase>

The crystal phase was specified by X-ray diffraction measurement. As arepresentative example, the result of the X-ray diffraction measurementof Reference Sample 15 is illustrated in FIG. 9. The lower chart in FIG.9 is a tungsten bronze type crystal phase serving as a reference andReference Sample 15 was confirmed to include the tungsten bronze typecrystal phase. The X-ray measurement results including other samples arelisted in Table 2, Table 4, and Table 6. The sign “T” in the tablesindicates that the existence of the tungsten bronze type crystal phasewas confirmed.

<Relative Dielectric Constant>

With respect to each of the capacitors, an electrostatic capacity C wasmeasured at a reference temperature of 25° C. using an LCR meter (4284A,manufactured by Agilent Technologies, Inc.) at a frequency of 1 kHz anda measurement voltage of 1 V_(rms). Thereafter, the relative dielectricconstant was calculated based on the thickness of the sintered compact,the effective electrode area, and the electrostatic capacity C obtainedby the measurement result. The relative dielectric constant at areference temperature of 200° C. was also calculated by the same manner.

A higher relative dielectric constant is preferable and thus thecapacitor having a relative dielectric constant of 100.0 or more at 25°C. is determined to be excellent.

<Change Rate in Electrostatic Capacity>

The electrostatic capacity C_(t) at each temperature t in thetemperature region of −55° C. to 200° C. was measured in the sameconditions as the conditions of the relative dielectric constantmeasurement (4284A, manufactured by Agilent Technologies, Inc.,frequency 1 kHz, and measurement voltage 1 V_(rms)). The change rate ofthe electrostatic capacity=((C_(t)−C₂₅)/C₂₅)×100(%) (hereinafter, thechange rate of the electrostatic capacity may be described asΔC_(t)/C₂₅) was calculated from the electrostatic capacity C₂₅ at 25° C.used as the reference.

The change rate of the electrostatic capacity is preferably closer to 0and is determined to be excellent when the change rate of theelectrostatic capacity is within ±50.0%.

With respect to Reference Samples 8, 15, and 66, the trends of thechange rate of the electrostatic capacity from −55° C. to 200° C. isillustrated in FIG. 6. In FIG. 6, the signs “x (cross)”, “◯ (circle)”,and “Δ (triangle)” refer to the change rate of the electrostaticcapacities of Reference Sample 8, Reference Sample 15, and ReferenceSample 66, respectively. With respect to Reference Samples 15 and 78,the trends of the change rate of the electrostatic capacity from −55° C.to 200° C. is illustrated in FIG. 7. In FIG. 7, the signs “◯ (circle)”and “Δ (tringle)” refer to the change rate of the electrostaticcapacities of Reference Sample 15 and Reference Sample 78, respectively.

<Dielectric Loss (Tan δ)>

With respect to each of the capacitor samples, tan δ was measured usingan LCR meter (4284A, manufactured by Agilent Technologies, Inc.) at afrequency of 1 kHz and a measurement voltage of 1 V_(rms). At 25° C. and200° C., tan δ is determined to be excellent when both of tan δ are10.0% or less.

TABLE 1 Second component composition in terms of oxides [% by mass]Total content First component composition in terms Oxide of Sample ofoxides [mol %] Dielectric ceramic component MnO second name CaO SrO BaOTiO₂ ZrO₂ SnO₂ Nb₂O₅ Ta₂O₅ V₂O₅ composition species content componentReference 33.33 0.00 16.67 16.67 0.00 0.00 33.33 0.00 0.00Ca₄Ba₂Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 1 Si, Y Reference 25.00 0.0025.00 16.67 0.00 0.00 33.33 0.00 0.00 Ca₃Ba₃Ti₂Nb₈O₃₀ Mg, Mn, 0.04480.765 Sample 2 Si, Y Reference 16.67 0.00 33.33 16.67 0.00 0.00 33.330.00 0.00 Ca₂Ba₄Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 3 Si, Y Reference4.17 0.00 45.83 16.67 0.00 0.00 33.33 0.00 0.00Ca_(0.5)Ba_(5.5)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 4 Si, Y Reference0.00 0.00 50.00 16.67 0.00 0.00 33.33 0.00 0.00 Ba₆Ti₂Nb₈O₃₀ Mg, Mn,0.0448 0.765 Sample 5 Si, Y Reference 16.67 8.33 25.00 16.67 0.00 0.0033.33 0.00 0.00 Ca₂SrBa₃Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 6 Si, YReference 0.00 8.33 41.67 16.67 0.00 0.00 33.33 0.00 0.00 SrBa₅Ti₂Nb₈O₃₀Mg, Mn, 0.0448 0.765 Sample 7 Si, Y Reference 16.67 16.67 16.67 16.670.00 0.00 33.33 0.00 0.00 Ca₂Sr₂Ba₂Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample8 Si, Y Reference 7.33 21.33 21.33 16.67 0.00 0.00 33.33 0.00 0.00Ca_(0.8)Sr_(2.6)Ba_(2.6)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 9 Si, YReference 0.00 25.00 25.00 16.67 0.00 0.00 33.33 0.00 0.00Sr₃Ba₃Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 10 Si, Y Reference 33.3316.67 0.00 16.67 0.00 0.00 33.33 0.00 0.00 Ca₄Sr₂Ti₂Nb₈O₃₀ Mg, Mn,0.0448 0.765 Sample 11 Si, Y Reference 8.33 33.33 8.33 16.67 0.00 0.0033.33 0.00 0.00 CaSr₄BaTi₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 12 Si, YReference 0.00 37.50 12.50 16.67 0.00 0.00 33.33 0.00 0.00Sr_(4.5)Ba_(1.5)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 13 Si, Y Reference8.33 41.67 0.00 16.67 0.00 0.00 33.33 0.00 0.00 CaSr₅Ti₂Nb₈O₃₀ Mg, Mn,0.0448 0.765 Sample 14 Si, Y Reference 16.67 33.33 0.00 16.67 0.00 0.0033.33 0.00 0.00 Ca₂Sr₄Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 15 Si, YReference 16.67 33.33 0.00 16.67 0.00 0.00 32.50 0.80 0.00Ca₂Sr₄Ti₂Nb_(7.8)Ta_(0.2)O₃₀ Mg, Mn, 0.0448 0.765 Sample 16 Si, YReference 16.67 33.33 0.00 16.67 0.00 0.00 26.60 6.70 0.00Ca₂Sr₄Ti₂Nb_(6.4)Ta_(1.6)O₃₀ Mg, Mn, 0.0448 0.765 Sample 17 Si, YReference 16.67 33.33 0.00 16.67 0.00 0.00 20.00 13.33 0.00Ca₂Sr₄Ti₂Nb_(4.8)Ta_(3.2)O₃₀ Mg, Mn, 0.0448 0.765 Sample 18 Si, YReference 16.67 33.33 0.00 16.67 0.00 0.00 13.33 20.00 0.00Ca₂Sr₄Ti₂Nb_(3.2)Ta_(4.8)O₃₀ Mg, Mn, 0.0448 0.765 Sample 19 Si, YReference 16.67 33.33 0.00 16.67 0.00 0.00 6.67 26.67 0.00Ca₂Sr₄Ti₂Nb_(1.6)Ta_(6.4)O₃₀ Mg, Mn, 0.0448 0.765 Sample 20 Si, YReference 16.67 33.33 0.00 16.67 0.00 0.00 0.00 33.33 0.00Ca₂Sr₄Ti₂Ta₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 21 Si, Y Reference 16.6733.33 0.00 15.00 1.67 0.00 33.33 0.00 0.00 Ca₂Sr₄Ti_(1.8)Zr_(0.2)Nb₈O₃₀Mg, Mn, 0.0448 0.765 Sample 22 Si, Y Reference 16.67 33.33 0.00 13.333.33 0.00 33.33 0.00 0.00 Ca₂Sr₄Ti_(1.6)Zr_(0.4)Nb₈O₃₀ Mg, Mn, 0.04480.765 Sample 23 Si, Y Reference 16.67 33.33 0.00 11.67 5.00 0.00 33.330.00 0.00 Ca₂Sr₄Ti_(1.4)Zr_(0.6)Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 24Si, Y Reference 16.67 33.33 0.00 10.00 6.67 0.00 33.33 0.00 0.00Ca₂Sr₄Ti_(1.2)Zr_(0.8)Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 25 Si, YReference 16.67 33.33 0.00 6.67 10.00 0.00 33.33 0.00 0.00Ca₂Sr₄Ti_(0.8)Zr_(1.2)Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 26 Si, YReference 16.67 33.33 0.00 3.33 13.33 0.00 33.33 0.00 0.00Ca₂Sr₄Ti_(0.4)Zr_(1.6)Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 27 Si, YReference 16.67 33.33 0.00 0.00 16.67 0.00 33.33 0.00 0.00Ca₂Sr₄Zr₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 28 Si, Y Reference 16.6733.33 0.00 16.50 0.00 0.17 33.33 0.00 0.00Ca₂Sr₄Ti_(1.98)Sn_(0.02)Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 29 Si, YReference 16.67 33.33 0.00 16.67 0.00 0.00 33.00 0.00 0.33Ca₂Sr₄Ti₂Nb_(7.96)V_(0.04)O₃₀ Mg, Mn, 0.0448 0.765 Sample 30 Si, Y

In Table 1, Table 3, and Table 5, the composition in terms of the oxideof the first component is represented by mol % of each of the oxides interms of the oxides listed in the tables relative to the total number ofmoles of each of the oxide components of the first component in terms ofthe oxides listed in the tables. The content of the Mn oxide isrepresented by % by mass of the Mn oxide in terms of MnO relative to thetotal mass of each of the oxide components of the first component interms of the oxides listed in the tables. The total content of theoxides of the second component is represented by % by mass of the totalof the oxides of the second component relative to the total mass of eachof the oxide components of the first component in terms of the oxidelisted in the tables.

TABLE 2 Change rate in Relative dielectric electrostatic capacity tan δSample Crystal Grain size constant [%] [%] name phase [μm] 25° C. 200°C. −55° C. 200° C. 25° C. 200° C. Reference T 1.4 101.1 104.2 −17.2 3.13.9 7.4 Sample 1 Reference T 0.8 214.2 252.1 −15.8 17.7 3.2 6.8 Sample 2Reference T 1.1 157.7 135.4 −15.4 −14.2 4.7 7.2 Sample 3 Reference T 0.9116.8 134.6 −9.6 15.2 3.7 7.8 Sample 4 Reference T 0.9 992.6 637.6 −29.335.8 1.8 8.5 Sample 5 Reference T 1.9 464.4 652.5 −30.0 40.5 2.6 4.5Sample 6 Reference T 1.8 249.4 202.2 9.8 −18.9 1.4 2.4 Sample 7Reference T 1.4 743.5 825.8 −23.9 11.1 2.2 8.8 Sample 8 Reference T 0.8146.0 153.5 7.9 5.2 1.7 3.7 Sample 9 Reference T 0.9 141.4 131.0 −5.0−7.4 5.6 8.5 Sample 10 Reference T 0.8 116.3 112.5 2.3 16.0 3.3 6.8Sample 11 Reference T 1.9 567.9 591.3 −17.0 4.1 2.3 4.0 Sample 12Reference T 0.9 242.0 270.9 −30.8 21.8 2.4 8.6 Sample 13 Reference T 2.0464.8 567.6 −8.6 22.1 2.8 8.1 Sample 14 Reference T 1.7 816.0 1,051.4−12.3 28.9 3.0 0.8 Sample 15 Reference T 2.5 437.6 525.3 −15.7 20.0 2.76.7 Sample 16 Reference T 1.8 875.3 674.3 −16.4 −23.0 0.9 1.1 Sample 17Reference T 1.0 663.1 474.4 −7.4 −28.4 1.8 1.4 Sample 18 Reference T 1.1413.8 270.3 25.6 −34.7 0.2 1.6 Sample 19 Reference T 1.4 315.8 229.234.5 −27.4 0.1 0.7 Sample 20 Reference T 1.1 241.1 191.6 22.8 −20.5 0.30.9 Sample 21 Reference T 2.9 495.6 607.4 −17.7 22.6 3.2 6.0 Sample 22Reference T 2.6 508.1 489.2 −17.5 −3.7 3.2 5.4 Sample 23 Reference T 2.1982.0 853.0 −23.1 −13.1 3.0 3.9 Sample 24 Reference T 2.7 873.8 732.4−16.6 −16.2 2.4 3.8 Sample 25 Reference T 1.2 411.5 326.6 2.6 −20.6 1.12.8 Sample 26 Reference T 1.6 832.5 691.9 −7.9 −16.9 0.9 3.5 Sample 27Reference T 1.2 320.9 247.3 1.9 −22.9 8.1 2.2 Sample 28 Reference T 1.8845.7 1,138.7 −23.9 34.6 3.2 2.8 Sample 29 Reference T 2.0 882.3 1,192.6−38.1 35.2 3.3 3.4 Sample 30

TABLE 3 First component composition in terms of Sample oxides [mol %]name CaO SrO BaO TiO₂ ZrO₂ SnO₂ Nb₂O₅ Ta₂O₅ V₂O₅ Reference 16.67 33.330.00 16.50 0.00 0.17 33.00 0.00 0.33 Sample 31 Reference 16.50 33.000.00 16.84 0.00 0.00 33.67 0.00 0.00 Sample 32 Reference 16.58 33.170.00 16.75 0.00 0.00 33.50 0.00 0.00 Sample 33 Reference 16.62 33.250.00 16.71 0.00 0.00 33.42 0.00 0.00 Sample 34 Reference 16.71 33.420.00 16.63 0.00 0.00 33.25 0.00 0.00 Sample 35 Reference 16.75 33.500.00 16.58 0.00 0.00 33.17 0.00 0.00 Sample 36 Reference 16.67 25.008.33 16.67 0.00 0.00 33.33 0.00 0.00 Sample 37 Reference 16.67 16.6716.67 16.67 0.00 0.00 31.67 1.67 0.00 Sample 38 Reference 0.00 16.6733.33 16.67 0.00 0.00 25.00 8.33 0.00 Sample 39 Reference 7.33 21.3321.33 16.67 0.00 0.00 25.00 8.33 0.00 Sample 40 Reference 16.67 33.330.00 16.67 0.00 0.00 33.33 0.00 0.00 Sample 41 Reference 16.67 33.330.00 16.67 0.00 0.00 33.33 0.00 0.00 Sample 42 Reference 16.67 33.330.00 16.67 0.00 0.00 33.33 0.00 0.00 Sample 43 Reference 16.67 33.330.00 16.67 0.00 0.00 33.33 0.00 0.00 Sample 44 Reference 16.67 33.330.00 16.67 0.00 0.00 33.33 0.00 0.00 Sample 45 Reference 33.33 8.33 8.3316.67 0.00 0.00 33.33 0.00 0.00 Sample 46 Reference 0.00 42.50 7.5016.67 0.00 0.00 33.33 0.00 0.00 Sample 47 Reference 5.00 45.00 0.0016.67 0.00 0.00 33.33 0.00 0.00 Sample 48 Reference 21.67 0.00 28.3316.67 0.00 0.00 33.33 0.00 0.00 Sample 49 Reference 27.50 2.50 20.0016.67 0.00 0.00 33.33 0.00 0.00 Sample 50 Reference 30.00 7.50 12.5016.67 0.00 0.00 33.33 0.00 0.00 Sample 51 Reference 30.00 12.50 7.5016.67 0.00 0.00 33.33 0.00 0.00 Sample 52 Reference 27.50 20.00 2.5016.67 0.00 0.00 33.33 0.00 0.00 Sample 53 Reference 25.00 25.00 0.0016.67 0.00 0.00 33.33 0.00 0.00 Sample 54 Reference 2.50 45.00 2.5016.67 0.00 0.00 33.33 0.00 0.00 Sample 55 Reference 3.33 33.33 13.3316.67 0.00 0.00 33.33 0.00 0.00 Sample 56 Reference 10.00 22.50 17.5016.67 0.00 0.00 33.33 0.00 0.00 Sample 57 Reference 13.33 18.33 18.3316.67 0.00 0.00 33.33 0.00 0.00 Sample 58 Reference 10.00 17.50 22.5016.67 0.00 0.00 33.33 0.00 0.00 Sample 59 Reference 3.33 18.33 28.3316.67 0.00 0.00 33.33 0.00 0.00 Sample 60 Second component compositionin terms of oxides [% by mass] Total content Oxide of Sample Dielectricceramic component MnO second name composition species content componentReference Ca₂Sr₄Ti_(1.98)Sn_(0.02)Nb_(7.96)V_(0.04)O₃₀ Mg, Mn, 0.04480.765 Sample 31 Si, Y Reference Ca_(1.96)Sr_(3.92)Ti₂Nb₈O₃₀ Mg, Mn,0.0448 0.765 Sample 32 Si, Y Reference Ca_(1.98)Sr_(3.96)Ti₂Nb₈O₃₀ Mg,Mn, 0.0448 0.765 Sample 33 Si, Y Reference Ca_(1.99)Sr_(3.98)Ti₂Nb₈O₃₀Mg, Mn, 0.0448 0.765 Sample 34 Si, Y ReferenceCa_(2.01)Sr_(4.02)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 35 Si, YReference Ca_(2.02)Sr_(4.04)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 36 Si,Y Reference Ca₂Sr₃BaTi₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 37 Si, YReference Ca₂Sr₂BaTi₂Nb_(7.6)Ta_(0.4)O₃₀ Mg, Mn, 0.0448 0.765 Sample 38Si, Y Reference Ca₂Ba₄Ti₂Nb₆Ta₂O₃₀ Mg, Mn, 0.0448 0.765 Sample 39 Si, YReference Ca_(0.8)Sr_(2.6)Ba_(2.6)Ti₂Nb₆Ta₂O₃₀ Mg, Mn, 0.0448 0.765Sample 40 Si, Y Reference Ca₂Sr₄Ti₂Nb₈O₃₀ Mg, Mn, 0.0010 0.721 Sample 41Si, Y Reference Ca₂Sr₄Ti₂Nb₈O₃₀ Mg, Mn, 0.4873 1.213 Sample 42 Si, YReference Ca₂Sr₄Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.531 Sample 43 Y ReferenceCa₂Sr₄Ti₂Nb₈O₃₀ Mn, Si, 0.0448 0.637 Sample 44 Y ReferenceCa₂Sr₄Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.407 Sample 45 Si ReferenceCa₄SrBaTi₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 46 Si, Y ReferenceSr_(5.1)Ba_(0.9)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 47 Si, Y ReferenceCa_(0.6)Sr_(5.4)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 48 Si, Y ReferenceCa_(2.6)Ba_(3.4)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 49 Si, Y ReferenceCa_(3.3)Sr_(0.3)Ba_(2.4)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 50 Si, YReference Ca_(3.6)Sr_(0.9)Ba_(1.5)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample51 Si, Y Reference Ca_(3.6)Sr_(1.5)Ba_(0.9)Ti₂Nb₈O₃₀ Mg, Mn, 0.04480.765 Sample 52 Si, Y Reference Ca_(3.3)Sr_(2.4)Ba_(0.3)Ti₂Nb₈O₃₀ Mg,Mn, 0.0448 0.765 Sample 53 Si, Y Reference Ca₃Sr₃Ti₂Nb₈O₃₀ Mg, Mn,0.0448 0.765 Sample 54 Si, Y Reference Ca_(0.3)Sr_(5.4)Ba_(0.3)Ti₂Nb₈O₃₀Mg, Mn, 0.0448 0.765 Sample 55 Si, Y ReferenceCa_(0.4)Sr₄Ba_(1.6)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 56 Si, YReference Ca_(1.2)Sr_(2.7)Ba_(2.1)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample57 Si, Y Reference Ca_(1.6)Sr_(2.2)Ba_(2.2)Ti₂Nb₈O₃₀ Mg, Mn, 0.04480.765 Sample 58 Si, Y Reference Ca_(1.2)Sr_(2.1)Ba_(2.7)Ti₂Nb₈O₃₀ Mg,Mn, 0.0448 0.765 Sample 59 Si, Y ReferenceCa_(0.4)Sr_(2.2)Ba_(3.4)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 60 Si, Y

TABLE 4 Change rate in Relative dielectric electrostatic capacity tan δSample Crystal Grain size constant [%] [%] name phase [μm] 25° C. 200°C. −55° C. 200° C. 25° C. 200° C. Reference T 2.2 912.8 1,296.2 −43.342.0 3.6 4.8 Sample 31 Reference T 1.8 551.8 734.6 −5.7 33.1 2.5 8.0Sample 32 Reference T 1.7 564.3 762.3 −6.0 35.1 2.6 7.4 Sample 33Reference T 1.8 532.9 730.5 −6.6 37.1 2.7 4.6 Sample 34 Reference T 1.9614.6 857.8 −5.7 39.6 2.4 6.0 Sample 35 Reference T 1.8 596.3 822.6 −6.437.9 2.6 5.3 Sample 36 Reference T 2.5 430.4 634.8 −14.4 47.5 1.9 6.8Sample 37 Reference T 0.9 637.1 707.6 −23.9 11.1 2.7 4.0 Sample 38Reference T 1.1 123.0 107.9 −15.3 −12.3 1.5 5.8 Sample 39 Reference T0.9 129.9 153.3 8.3 5.8 1.5 6.0 Sample 40 Reference T 2.3 702.7 1,140.3−5.7 42.3 2.3 8.6 Sample 41 Reference T 2.6 200.4 206.2 −33.1 48.1 4.79.8 Sample 42 Reference T 2.1 624.4 922.7 −3.9 47.8 2.1 6.8 Sample 43Reference T 2.3 630.8 1,161.1 −2.8 44.1 1.9 8.8 Sample 44 Reference T2.0 776.2 1,350.6 0.3 34.0 1.5 3.7 Sample 45 Reference T 1.1 205.4 210.510.2 9.5 3.6 7.1 Sample 46 Reference T 0.8 208.3 205.4 −21.9 10.6 2.68.9 Sample 47 Reference T 2.1 294.8 397.6 −12.3 26.1 3.8 9.1 Sample 48Reference T 1.0 206.7 244.3 −13.4 −12.2 2.3 3.6 Sample 49 Reference T1.1 220.2 258.9 −12.9 13.7 2.1 3.1 Sample 50 Reference T 1.3 231.4 270.1−12.5 13.1 1.9 2.8 Sample 51 Reference T 1.2 243.6 281.3 −11.4 12.8 1.72.5 Sample 52 Reference T 0.9 201.3 206.5 −5.9 8.1 1.6 3.4 Sample 53Reference T 1.0 209.6 201.3 −6.6 −8.6 2.8 5.1 Sample 54 Reference T 1.8315.3 418.1 −10.5 20.2 3.2 8.1 Sample 55 Reference T 1.4 401.4 435.2−23.4 13.0 2.3 6.3 Sample 56 Reference T 1.1 215.3 204.9 5.9 3.2 1.1 3.1Sample 57 Reference T 1.2 424.5 410.3 2.8 1.6 0.6 1.5 Sample 58Reference T 1.3 224.7 212.8 5.4 2.8 1.2 3.4 Sample 59 Reference T 1.2206.1 213.6 5.8 3.1 0.9 1.8 Sample 60

TABLE 5 Second component composition in terms of oxides [% by mass]Total content First component composition in terms of Oxide of Sampleoxides [mol %] Dielectric ceramic component MnO second name CaO SrO BaOTiO₂ ZrO₂ SnO₂ Nb₂O₅ Ta₂O₅ V₂O₅ composition species content componentReference 0.00 17.50 32.50 16.67 0.00 0.00 33.33 0.00 0.00Sr_(2.1)Ba_(3.9)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 61 Si, Y Reference6.67 6.67 36.67 16.67 0.00 0.00 33.33 0.00 0.00Ca_(0.8)Sr_(0.8)Ba_(4.4)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 62 Si, YReference 1.67 5.00 43.33 16.67 0.00 0.00 33.33 0.00 0.00Ca_(0.2)Sr_(0.6)Ba_(5.2)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 63 Si, YReference 17.50 2.50 30.00 16.67 0.00 0.00 33.33 0.00 0.00Ca_(2.1)Sr_(0.3)Ba_(3.6)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 64 Si, YReference 50.00 0.00 0.00 16.67 0.00 0.00 33.33 0.00 0.00 Ca₆Ti₂Nb₈O₃₀Mg, Mn, 0.0448 0.765 Sample 65 Si, Y Reference 40.00 5.00 5.00 16.670.00 0.00 33.33 0.00 0.00 Ca_(4.8)Sr_(0.6)Ba_(0.6)Ti₂Nb₈O₃₀ Mg, Mn,0.0448 0.765 Sample 66 Si, Y Reference 0.00 50.00 0.00 16.67 0.00 0.0033.33 0.00 0.00 Sr₆Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 67 Si, YReference 0.00 0.00 50.00 0.00 0.00 0.00 50.00 0.00 0.00 BaNb₂O₆ Mg, Mn,0.0448 0.765 Sample 68 Si, Y Reference 0.00 50.00 0.00 0.00 0.00 0.0050.00 0.00 0.00 SrNb₂O₆ Mg, Mn, 0.0448 0.765 Sample 69 Si, Y Reference50.00 0.00 0.00 0.00 0.00 0.00 50.00 0.00 0.00 CaNb₂O₆ Mg, Mn, 0.04480.765 Sample 70 Si, Y Reference 0.00 0.00 48.28 17.24 0.00 0.00 34.480.00 0.00 Ba_(5.6)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 71 Si, YReference 0.00 0.00 51.61 16.13 0.00 0.00 32.26 0.00 0.00Ba_(6.4)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 72 Si, Y Reference 16.0632.12 0.00 17.27 0.00 0.00 34.54 0.00 0.00 Ca_(1.86)Sr_(3.72)Ti₂Nb₈O₃₀Mg, Mn, 0.0448 0.765 Sample 73 Si, Y Reference 17.12 34.41 0.00 16.160.00 0.00 32.31 0.00 0.00 Ca_(2.12)Sr_(4.26)Ti₂Nb₈O₃₀ Mg, Mn, 0.04480.765 Sample 74 Si, Y Reference 16.67 33.33 0.00 13.33 0.00 3.33 33.330.00 0.00 Ca₂Sr₄Ti_(1.6)Sn_(0.4)Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 75Si, Y Reference 16.67 33.33 0.00 16.67 0.00 0.00 30.00 0.00 3.33Ca₂Sr₄Ti₂Nb_(7.2)V_(0.8)O₃₀ Mg, Mn, 0.0448 0.765 Sample 76 Si, YReference 16.67 33.33 0.00 15.00 0.00 1.67 30.00 0.00 3.33Ca₂Sr₄Ti_(1.8)Sn_(0.2)Nb_(7.2)V_(0.8)O₃₀ Mg, Mn, 0.0448 0.765 Sample 77Si, Y Reference 16.67 33.33 0.00 16.67 0.00 0.00 33.33 0.00 0.00Ca₂Sr₄Ti₂Nb₈O₃₀ Mg, Si, 0.0000 0.720 Sample 78 Y Reference 16.67 16.6716.67 16.67 0.00 0.00 33.33 0.00 0.00 Ca₂Sr₂Ba₂Ti₂Nb₈O₃₀ Mg, Si, 0.00000.720 Sample 79 Y Reference 16.67 33.33 0.00 16.67 0.00 0.00 33.33 0.000.00 Ca₂Sr₄Ti₂Nb₈O₃₀ Mg, Mn, 5.0710 5.791 Sample 80 Si, Y Reference37.50 12.50 0.00 16.67 0.00 0.00 33.33 0.00 0.00Ca_(4.5)Sr_(1.5)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 81 Si, Y Reference37.50 0.00 12.50 16.67 0.00 0.00 33.33 0.00 0.00Ca_(4.5)Ba_(1.5)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 82 Si, Y Reference0.00 47.50 2.50 16.67 0.00 0.00 33.33 0.00 0.00Sr_(5.7)Ba_(0.3)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 83 Si, Y Reference36.67 6.67 6.67 16.67 0.00 0.00 33.33 0.00 0.00Ca_(4.4)Sr_(0.8)Ba_(0.8)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 84 Si, YReference 37.50 10.00 2.50 16.67 0.00 0.00 33.33 0.00 0.00Ca_(4.5)Sr_(1.2)Ba_(0.3)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 85 Si, YReference 37.50 2.50 10.00 16.67 0.00 0.00 33.33 0.00 0.00Ca_(4.5)Sr_(0.3)Ba_(1.2)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 86 Si, YReference 30.00 0.00 20.00 16.67 0.00 0.00 33.33 0.00 0.00Ca_(3.6)Ba_(2.4)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 87 Si, Y Reference6.67 1.67 41.67 16.67 0.00 0.00 33.33 0.00 0.00Ca_(0.8)Sr_(0.2)Ba₅Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 88 Si, YReference 0.00 32.50 17.50 16.67 0.00 0.00 33.33 0.00 0.00Sr_(3.9)Ba_(2.1)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 89 Si, Y Reference0.00 22.50 27.50 16.67 0.00 0.00 33.33 0.00 0.00Sr_(2.7)Ba_(3.3)Ti₂Nb₈O₃₀ Mg, Mn, 0.0448 0.765 Sample 90 Si, Y

TABLE 6 Change rate in Relative dielectric electrostatic capacity tan δSample Crystal Grain size constant [%] [%] name phase [μm] 25° C. 200°C. −55° C. 200° C. 25° C. 200° C. Reference T 1.7 231.4 245.3 7.5 −16.41.1 2.1 Sample 61 Reference T 1.8 238.2 215.4 12.6 −22.3 2.1 3.6 Sample62 Reference T 1.4 459.5 345.2 −19.7 26.5 1.5 4.4 Sample 63 Reference T1.5 311.1 394.4 −22.7 27.4 3.7 5.9 Sample 64 Reference T 0.5 44.0 61.7−18.9 40.3 5.1 10.9 Sample 65 Reference T 0.6 135.1 244.5 −12.9 81.0 2.227.2 Sample 66 Reference T 0.7 86.8 84.4 −12.9 −2.8 2.8 14.6 Sample 67Reference T 1.8 51.7 482.7 1.2 833.3 5.6 56.1 Sample 68 Reference T 1.6101.6 54.3 −52.2 −46.5 39.4 0.1 Sample 69 Reference T 0.9 57.1 43.0−24.6 −24.7 26.7 0.1 Sample 70 Reference T 1.3 611.6 994.7 −6.6 62.6 2.118.8 Sample 71 Reference T 1.2 715.3 997.4 −7.0 39.4 2.3 14.6 Sample 72Reference T 2.3 717.7 957.7 −6.2 33.4 2.5 11.7 Sample 73 Reference T 3.1525.0 757.2 −4.1 44.2 2.8 16.8 Sample 74 Reference T 2.5 986.8 4,909.9−23.7 397.5 3.7 84.3 Sample 75 Reference T 2.4 2,555.1 N.D. N. D. N.D.64.0 N. D. Sample 76 Reference T 4.1 1,269.0 2,886.4 −50.7 127.5 28.790.9 Sample 77 Reference T 2.2 713.2 1,158.0 −5.4 62.4 2.8 18.9 Sample78 Reference T 1.9 310.4 335.2 −10.5 59.6 6.5 15.8 Sample 79 Reference T2.8 257.2 281.5 −15.7 62.3 9.8 12.1 Sample 80 Reference T 0.7 125.2183.4 −10.3 61.1 2.9 17.0 Sample 81 Reference T 2.0 80.3 83.4 −19.1 30.24.6 10.1 Sample 82 Reference T 0.8 94.8 92.4 −25.8 −4.9 5.6 21.5 Sample83 Reference T 0.7 102.5 133.6 −7.5 60.5 3.3 13.4 Sample 84 Reference T0.8 113.8 158.5 −8.6 60.8 3.1 15.2 Sample 85 Reference T 1.4 90.4 108.5−13.6 50.6 3.9 11.8 Sample 86 Reference T 1.6 102.9 106.1 −22.9 6.1 4.17.7 Sample 87 Reference T 1.1 180.1 189.8 −14.5 20.1 5.0 9.1 Sample 88Reference T 1.5 188.9 175.3 6.6 3.8 4.9 7.8 Sample 89 Reference T 1.2171.4 162.6 −4.5 −6.9 5.1 8.0 Sample 90

(3) Evaluation

From the above-described results, the samples existing within the rangesurrounded by the line segments of A-B-C-D-E in FIG. 1 had relativedielectric constants at 25° C. of 100.0 or more. In other words, it wasconfirmed that these samples had ferroelectricity. The samples existingwithin the range surrounded by the line segments of A-B-C-D-E in FIG. 1also had change rates in electrostatic capacities of within ±50.0% inthe temperature range of −55° C. to 200° C. and dielectric losses (tanδ) at 25° C. and 200° C. of 10.0% or less.

Furthermore, the samples existing within the range surrounded by theline segments of point A′-point B′-point C′-point D′-point E′-pointF′-point G′-point Er-point I′-point J′-point K′-point L′ in FIG. 2 hadrelative dielectric constants at 25° C. of 200 or more.

Of these samples, the samples of Reference Sample Numbers 5, 8, 12, 15,17, 18, 23 to 25, 27, 29 to 36, 38, 41, and 43 to 45 indicated relativedielectric constants of 500.0 or more and thus are particularlypreferable.

The samples of Reference Sample Numbers 1 to 4, 7 to 13, 16 to 18, 23 to28, 38 to 40, 46, 47, 49 to 62, and 87 to 90 indicated change rates inelectrostatic capacities ΔC_(t)/C₂₅ in the temperature region of −55° C.to 200° C. of −33.0% to +22.0% and thus are particularly excellent intemperature properties.

In contrast to these samples, the samples of Reference Sample Numbers 65to 86 did not provide excellent properties about one or moreperformances of the relative dielectric constant, the change rate of theelectrostatic capacity, and tan δ.

As illustrated in FIG. 6, it is found that the change rate of theelectrostatic capacity is within the range of −30.0% to 30.0% in thetemperature range of −55° C. to 200° C. in the case where ReferenceSamples 8 and 15 are used, whereas the change rate of the electrostaticcapacity is remarkably increased over around 150° C. in the case ofReference Sample 66.

Reference Sample 15 and Reference Sample 78 are samples that only hasdifference in the presence or absence of the oxide of Mn as the secondcomponent. As illustrated in FIG. 7, it is found that properties of bothsamples are significantly different.

Reference Example 2

The Reference Samples 91 to 107 were prepared in the same method as themethod in Reference Sample 1 except that the raw materials for the firstcomponent described above were weighed so that the compositions in termsof the oxides were as listed in Table 7 and MnCO₃ and SiO₂ were weighedas the second component so that the compositions in terms of the oxideswere as listed in Table 7. The disk-shaped ceramic capacitorscorresponding to each of the samples were provided.

Thereafter, similar to Reference Example 1, the grain size, the crystalphase, the relative dielectric constant, the change rate of theelectrostatic capacity, and the dielectric loss (tan δ) were measured.The results are listed in Table 8.

From these results, it is found that the samples having the Mn contentin terms of MnO serving as the second component of less than 3.500% bymass relative to the total mass of the first component in terms of theoxides provide excellent results with respect to the relative dielectricconstant, the change rate of the electrostatic capacity, and tan δ.

TABLE 7 First component composition in terms of Sample oxides [mol %]Dielectric ceramic name CaO SrO BaO TiO₂ ZrO₂ SnO₂ Nb₂O₅ Ta₂O₅ V₂O₅composition Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 91Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 92Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 93Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 94Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 95Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 96Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 97Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 98Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 99Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 100Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 101Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 102Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 103Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 104Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 105Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 106Reference 12.50 33.30 4.16 15.03 1.67 0.00 29.97 3.33 0.00Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 107 Secondcomponent composition in terms of oxides [% by mass] Total content Oxideof Sample component MnO second name species content component ReferenceMn, Si 0.617 0.917 Sample 91 Reference Mn, Si 0.9258 1.226 Sample 92Reference Mn, Si 1.2344 1.534 Sample 93 Reference Mn, Si 3.0860 3.386Sample 94 Reference Mn, Si 3.3946 3.695 Sample 95 Reference Mn, Si3.6414 3.941 Sample 96 Reference Mn, Si 0.9258 1.426 Sample 97 ReferenceMn, Si 1.2344 1.734 Sample 98 Reference Mn, Si 3.0860 3.586 Sample 99Reference Mn, Si 3.3946 3.895 Sample 100 Reference Mn, Si 3.6414 4.141Sample 101 Reference Mn, Si 0.6172 1.317 Sample 102 Reference Mn, Si0.9258 1.626 Sample 103 Reference Mn, Si 1.2344 1.934 Sample 104Reference Mn, Si 3.0860 3.786 Sample 105 Reference Mn, Si 3.3946 4.095Sample 106 Reference Mn, Si 3.6414 4.341 Sample 107

In Table 7, the composition in terms of the oxide of the first componentis represented by mol % of each of the oxides in terms of the oxideslisted in Table 7 relative to the total number of moles of each of theoxide components of the first component in terms of the oxides listed inTable 7. The content of the Mn oxide is represented by % by mass of theMn oxide in terms of MnO relative to the total mass of each of the oxidecomponents of the first component in terms of the oxides listed in Table7. The total content of the oxides of the second component isrepresented by % by mass of the total of the oxides of the secondcomponent relative to the total mass of each of the oxide components ofthe first component in terms of the oxide listed in Table 7.

TABLE 8 Change rate in Relative dielectric electrostatic capacity tan δSample Crystal Grain size constant [%] [%] name phase [μm] 25° C. 200°C. −55° C. 200° C. 25° C. 200° C. Reference T 1.5 965.7 932.3 −17.0 −3.51.5 1.6 Sample 91 Reference T 1.8 953.9 921.4 −18.7 −3.4 1.3 5.2 Sample92 Reference T 1.5 886.3 687.2 −18.7 −22.5 4.0 1.6 Sample 93 Reference T1.6 869.5 750.6 −17.6 −13.7 1.8 5.6 Sample 94 Reference T 1.8 842.6631.8 −16.2 −20.3 2.2 8.3 Sample 95 Reference T 2.0 767.1 582.4 −12.3−27.9 2.8 12.4 Sample 96 Reference T 2.5 981.3 935.7 −19.1 −4.6 1.5 2.4Sample 97 Reference T 2.2 1,011.8 985.1 −20.6 −2.6 2.0 2.1 Sample 98Reference T 1.6 805.1 713.3 −17.5 −11.4 1.2 6.3 Sample 99 Reference T1.5 738.6 573.3 −16.3 −18.2 2.3 9.5 Sample 100 Reference T 1.3 627.8446.6 −15.8 −30.7 2.7 15.8 Sample 101 Reference T 1.3 988.6 952.3 −20.7−3.7 2.3 1.2 Sample 102 Reference T 3.5 973.5 924.6 −20.8 −5.0 2.1 2.3Sample 103 Reference T 4.4 972.1 921.3 −21.2 −5.2 1.8 1.9 Sample 104Reference T 4.5 804.0 717.7 −18.8 −10.7 2.1 7.1 Sample 105 Reference T4.8 725.2 586.3 −17.2 −16.9 2.6 9.8 Sample 106 Reference T 5.1 584.7488.1 −14.4 −29.3 2.9 17.2 Sample 107

From the above-described results, from comparison with the samples inwhich the content of the first component is out of the defined amount ofthe present invention or the samples in which the content of the oxideof Mn is out of the defined amount of the present invention, the samplesin which the content of the first component is in the defined amount ofthe present invention, the content of the oxide of Mn is in the definedamount of the present invention, and the oxide of Cu and the oxide of Ruare not included exhibit effects of a small change in the electrostaticcapacity even under a high temperature condition of 150° C. to 200° C.,the change rate of the electrostatic capacity within the range of −50.0%to 50.0% in a temperature range of −55° C. to 200° C., and smalldielectric losses at 25° C. and 200° C.

Example 1 and Comparative Example 1

(1) Preparation of Dielectric Ceramic Composition Samples 1 to 20

As the starting materials of the first component, each powder of CaCO₃,SrCO₃, BaCO₃, TiO₂, ZrO₂, Nb₂O₅, and Ta₂O₅ was weighed so that the ratioof each powder in terms of the oxides was as listed in Table 9 and theresultant mixture was wet-blended for 20 hours with pure water using aball mill.

Subsequently, each of the blends was dried at 100° C. and thereaftercalcinated at 750° C. to 900° C. for 3 hours in the air. The obtainedproduct was similarly finely pulverized again with the ball mill toprepare the dielectric raw material for the first component.

As the second component, a mixture made by weighing and mixing 41.2 mgof MnCO₃, 72.2 mg of MgO, and 53.9 mg of SiO₂ was provided and thismixture was used as the raw material for second component. Here, the rawmaterial for second component was used in an amount of 1.3 times in eachof Samples 1 to 6, 8, 9, 11, and 15 to 19. In Samples 8 to 11 and 15 to20, in addition to the above-described raw materials, as the rawmaterial for the second component, CuO was provided in 0.036% by mass to0.680% by mass relative to the total mass of each of the oxides of thefirst component in terms of the oxides listed in the tables. In Samples12 to 14, in addition to the above-described raw materials, as the rawmaterial for the second component, RuO₂ was provided in 0.100% by massto 0.500% by mass relative to the total mass of each of the oxides ofthe first component in terms of the oxide listed in the tables.

A poly(vinyl alcohol) aqueous solution was prepared by chargingion-exchanged water and poly(vinyl alcohol) in a container so that thepoly(vinyl alcohol) concentration was 6% by mass and mixing theresultant mixture at 90° C. for 1 hour.

Then, 25 g of each of the dielectric raw materials for the firstcomponent and the raw material for the second component having theabove-described amount were mixed. The poly(vinyl alcohol) aqueoussolution was added to the raw material mixture so that the concentrationof the poly(vinyl alcohol) aqueous solution was 10% by mass relative tothe resultant mixture and the resultant product was mixed and granulatedin a mortar to prepare a granulated powder.

Furthermore, the obtained granulated powder was charged in a mold havinga diameter of 14.0 mm and press-molded at a pressure of 1 ton/cm² toprovide a disk-shaped green compact.

Subsequently, the obtained green compact was fired in a reducingatmosphere to prepare a sintered compact. In this firing, thetemperature increasing rate, the holding temperature, and the holdingtime were set to 300° C./h, 1,100° C. to 1,300° C., and two hours,respectively. As an atmosphere gas, moistened hydrogen/nitrogen mixturegas (hydrogen concentration 0.5%) was used and a wetter (wettertemperature 35° C.) was used for the moistening.

<Insulation Resistance Value>

For each of the capacitor samples, the insulation resistance value wasmeasured using a digital ultra-high resistance meter/microammeter(8340A, manufactured by ADC CORPORATION) at an applied voltage of 200 V.The insulation resistance value was determined to be excellent when theinsulation resistance value is 40 MΩ or more at 200° C.

TABLE 9 First component composition in terms of Sample oxides [mol %]Dielectric ceramic name CaO SrO BaO TiO₂ ZrO₂ Nb₂O₅ Ta₂O₅ compositionSample 1 12.50 33.33 4.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 2 25.0025.00 0.00 15.00 1.67 28.75 4.58Ca₃Sr₃Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀ Sample 3 0.00 5.00 45.00 15.001.67 28.75 4.58 Sr_(0.6)Ba_(5.4)Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀Sample 4 8.33 16.67 25.00 15.00 1.67 28.75 4.58CaSr₂Ba₃Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀ Sample 5 30.00 10.00 10.0015.00 1.67 28.75 4.58Ca_(3.6)Sr_(1.2)Ba_(1.2)Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀ Sample 60.00 42.50 7.50 15.00 1.67 28.75 4.58Sr_(5.1)Ba_(0.9)Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀ Sample 7 12.50 33.334.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 8 12.5033.33 4.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 9 12.5033.33 4.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 10 12.5033.33 4.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 11 12.5033.33 4.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 12 12.5033.33 4.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 13 12.5033.33 4.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 14 12.5033.33 4.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Sample 15 25.0025.00 0.00 15.00 1.67 28.75 4.58Ca₃Sr₃Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀ Sample 16 0.00 5.00 45.0015.00 1.67 28.75 4.58Sr_(0.6)Ba_(5.4)Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀ Sample 17 8.33 16.6725.00 15.00 1.67 28.75 4.58 CaSr₂Ba₃Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀Sample 18 30.00 10.00 10.00 15.00 1.67 28.75 4.58Ca_(3.6)Sr_(1.2)Ba_(1.2)Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀ Sample 190.00 42.50 7.50 15.00 1.67 28.75 4.58Sr_(5.1)Ba_(0.9)Ti_(1.8)Zr_(0.2)Nb_(6.9)Ta_(1.1)O₃₀ Sample 20 12.5033.33 4.17 15.00 1.67 30.00 3.33Ca_(1.5)Sr₄Ba_(0.5)Ti_(1.8)Zr_(0.2)Nb_(7.2)Ta_(0.8)O₃₀ Second componentcomposition in terms of oxides [% by mass] Total content Oxide of Samplecomponent MnO CuO RuO₂ second name species content content contentcomponent Sample 1 Mg, Mn, 0.132 0.000 0.000 0.991 Si Sample 2 Mg, Mn,0.132 0.000 0.000 0.991 Si Sample 3 Mg, Mn, 0.132 0.000 0.000 0.991 SiSample 4 Mg, Mn, 0.132 0.000 0.000 0.991 Si Sample 5 Mg, Mn, 0.132 0.0000.000 0.991 Si Sample 6 Mg, Mn, 0.132 0.000 0.000 0.991 Si Sample 7 Mg,Mn, 0.102 0.000 0.000 0.762 Si Sample 8 Mg, Mn, 0.132 0.036 0.000 1.027Si, Cu Sample 9 Mg, Mn, 0.132 0.045 0.000 1.036 Si, Cu Sample 10 Mg, Mn,0.102 0.050 0.000 0.812 Si, Cu Sample 11 Mg, Mn, 0.132 0.054 0.000 1.045Si, Cu Sample 12 Mg, Mn, 0.102 0.000 0.100 0.862 Si, Ru Sample 13 Mg,Mn, 0.102 0.000 0.200 0.962 Si, Ru Sample 14 Mg, Mn, 0.102 0.000 0.5001.262 Si, Ru Sample 15 Mg, Mn, 0.132 0.677 0.000 1.667 Si, Cu Sample 16Mg, Mn, 0.132 0.677 0.000 1.667 Si, Cu Sample 17 Mg, Mn, 0.132 0.6770.000 1.667 Si, Cu Sample 18 Mg, Mn, 0.132 0.677 0.000 1.667 Si, CuSample 19 Mg, Mn, 0.132 0.677 0.000 1.667 Si, Cu Sample 20 Mg, Mn, 0.1020.100 0.000 0.862 Si, Cu

In Table 9, the composition in terms of the oxide of the first componentis represented by mol % of each of the oxides in terms of the oxideslisted in the tables relative to the total number of moles of each ofthe oxide components of the first component in terms of the oxideslisted in Table 9. The content of the Mn oxide is represented by % bymass of the Mn oxide in terms of MnO relative to the total mass of eachof the oxide components of the first component in terms of the oxideslisted in Table 9. The content of the Cu oxide is represented by % bymass of the Cu oxide in terms of CuO relative to the total mass of eachof the oxide components of the first component in terms of the oxideslisted in Table 9. The content of the Ru oxide is represented by % bymass of the Ru oxide in terms of RuO₂ relative to the total mass of eachof the oxide components of the first component in terms of the oxideslisted in Table 9. The total content of the oxides of the secondcomponent is represented by % by mass of the total of the oxides of thesecond component relative to the total mass of each of the oxidecomponents of the first component in terms of the oxide listed in Table9.

TABLE 10 Insulation Change rate in resistance Relative dielectricelectrostatic capacity tan δ value Sample constant [%] [%] [MΩ] name 25°C. 200° C. −55° C. 200° C. 25° C. 200° C. 200° C. Sample 1 865.5 923.9−18.3 6.8 1.9 6.2 26 Sample 2 662.0 660.7 −22.7 −0.2 2.7 4.9 8.30 Sample3 586.3 413.3 20.7 −29.5 0.8 2.4 35.7 Sample 4 1,061.9 601.9 −9.4 −43.30.9 4.2 14.7 Sample 5 511.0 453.3 −24.8 −11.3 2.2 5.0 8.62 Sample 61,234.2 680.1 2.0 −44.9 1.1 6.2 9.5 Sample 7 901.3 856.9 −29.2 −4.9 1.87.0 18 Sample 8 824.9 840.2 −16.3 1.9 1.1 3.6 64 Sample 9 798.7 818.2−18.3 2.4 1.7 4.8 60 Sample 10 805.8 789.7 −17.9 −2.0 1.6 3.0 80 Sample11 774.9 809.5 −17.9 4.5 1.6 6.1 40 Sample 12 663.0 677.7 −17.9 2.2 1.45.7 47 Sample 13 676.1 626.6 −19.1 −7.3 1.6 2.9 93 Sample 14 718.9 712.1−20.0 −0.9 1.6 4.5 208 Sample 15 622.0 460.5 −27.2 −26.0 2.9 6.3 211Sample 16 644.1 485.7 20.7 −24.6 0.7 7.0 309 Sample 17 1,115.0 634.1−11.3 −43.1 1.3 4.8 277 Sample 18 606.8 460.3 −23.0 −24.1 3.2 3.6 189Sample 19 1,178.6 648.1 4.9 −45.0 1.3 3.6 371 Sample 20 855.8 817.0−14.8 −4.5 1.2 2.6 1,694

From the above-described results, it is confirmed that the content ofthe first component is in the defined amount of the present invention,the oxide of Mn is included in the defined amount of the presentinvention, and one or both of the oxide of Cu and the oxide of Ru areincluded, whereby a high relative dielectric constant at 25° C., a smallchange in the electrostatic capacity even under a high temperaturecondition of 150° C. to 200° C., the change rate of the electrostaticcapacity within the range of −50.0% to 50.0% in a temperature range of−55° C. to 200° C., small dielectric losses at 25° C. and 200° C., andthe high insulation resistance value at 200° C. can be achieved.

From the comparison with the Reference Samples in which the content ofthe first component is in the range of the defined amount of the presentinvention and the content of the oxide of Mn is in the defined amount ofthe present invention, but the oxide of Cu and the oxide of Ru are notincluded, it is found that the content of the first component is in therange of the defined amount of the present invention, the oxide of Mn isincluded in the range of the defined amount of the present invention,and one or both of the oxide of Cu and the oxide of Ru are included,whereby the insulation resistance value can be increased while thechange in the electrostatic capacity is further smaller withoutsignificantly affecting action and effect on the relative dielectricconstant, the change rate of the electrostatic capacity, and thedielectric loss.

In the above-described example, the single-plate type ceramic capacitorshave been evaluated. For a laminated ceramic capacitor in whichdielectric layers and internal electrodes are laminated, similar resultscan also be obtained.

REFERENCE CHARACTERS LIST

-   -   1 Laminated Ceramic Capacitor    -   2 Dielectric Layer    -   3 Internal Electrode Layer    -   4 External Electrode    -   10 Laminated body

1. A dielectric ceramic composition comprising: a first component; and a second component, wherein as a content ratio relative to a total number of moles of the first component when converted into following oxides, the first component comprises an oxide of Ca of 0.00 mol % to 35.85 mol % in terms of CaO, an oxide of Sr of 0.00 mol % to 47.12 mol % in terms of SrO, an oxide of Ba of 0.00 mol % to 51.22 mol % in terms of BaO, an oxide of Ti of 0.00 mol % to 17.36 mol % in terms of TiO₂, an oxide of Zr of 0.00 mol % to 17.36 mol % in terms of ZrO₂, an oxide of Sn of 0.00 mol % to 2.60 mol % in terms of SnO₂, an oxide of Nb of 0.00 mol % to 35.32 mol % in terms of Nb₂O₅, an oxide of Ta of 0.00 mol % to 35.32 mol % in terms of Ta₂O₅, and an oxide of V of 0.00 mol % to 2.65 mol % in terms of V₂O₅; the first component comprises at least one oxide selected from the oxide of Ca, the oxide of Sr, and the oxide of Ba, at least one oxide selected from the oxide of Ti and the oxide of Zr, and at least one oxide selected from the oxide of Nb and the oxide of Ta as essential components, and a total content ratio of the oxide of Ca in terms of CaO, the oxide of Sr in terms of SrO, and the oxide of Ba in terms of BaO is 48.72 mol % to 51.22 mol %, a total content ratio of the oxide of Ti in terms of TiO₂, the oxide of Zr in terms of ZrO₂, and the oxide of Sn in terms of SnO₂ is 15.97 mol % to 17.36 mol %, and a total content ratio of the oxide of Nb in terms of Nb₂O₅, the oxide of Ta in terms of Ta₂O₅, and the oxide of V in terms of V₂O₅ is 31.42 mol % to 35.31 mol % relative to the total number of moles of the first component when converted into the oxides; and as a content ratio relative to a total mass of the first component when converted into the oxides, the second component comprises at least (a) an oxide of Mn of 0.005% by mass to 3.500% by mass in terms of MnO and (b) one or both of an oxide of Cu and an oxide of Ru.
 2. A dielectric ceramic composition comprising: a first component; and a second component, wherein as the first component, a compound represented by a following general formula (1): A_(a)M¹ _(b)M² _(c)O_(d)  (1) (in the formula (1), A is represented by a general formula (2): Ba_(1-x-y)Sr_(x)Ca_(y)  (2) (in the formula (2), 0≤x≤0.920 and 0≤y≤0.700); M¹ is at least one element selected from Ti, Zr, and Sn; M² is at least one element selected from Nb, Ta, and V; and 5.70≤a≤6.30, 1.90≤b≤2.10, 7.20≤c≤8.80, and 27.45≤d≤32.50) is included (with the proviso that, when Sn is included, a content ratio of the oxide of Sn in terms of SnO₂ relative to a total number of moles of the oxide of Ti in terms of TiO₂, the oxide of Zr in terms of ZrO₂, and the oxide of Sn in terms of SnO₂ is 15.00 mol % or less and when V is included, a content ratio of the oxide of V in terms of V₂O₅ relative to a total number of moles of the oxide of Nb in terms of Nb₂O₅, the oxide of Ta in terms of Ta₂O₅, and the oxide of V in terms of V₂O₅ is 7.50 mol % or less); and as a content ratio relative to a total mass of the first component when the first component is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅, Ta₂O₅, and V₂O₅, the second component comprises at least (a) an oxide of Mn of 0.005% by mass to 3.500% by mass in terms of MnO and (b) one or both of an oxide of Cu and an oxide of Ru.
 3. A dielectric ceramic composition comprising: a first component; and a second component, wherein a compound represented by a following general formula (3): α·Ca_(η1)M³ _(θ1)M⁴ _(ϕ1)O_(ω1)-β·Sr_(η2)M³ _(θ2)M⁴ _(ϕ2)O_(ω2-γ)·Ba_(η3)M³ _(θ3)M⁴ _(ϕ3)O_(ω3)  (3) (in the formula (3), η1, η2, and η3 are each independently values within a range of 5.70 to 6.30; θ1, θ2, and θ3 are each independently values within a range of 0.95 to 1.05; ϕ1, ϕ2, and ϕ3 are each independently values within a range of 0.90 to 1.10; ω1, ω2, and ω3 are each independently values within a range of 27.45 to 32.50; M³ is represented by a general formula (4): Ti_(2-ρ-σ)Zr_(ρ)Sn_(σ)  (4) (in the formula (4), 0≤ρ≤2.0 and 0≤σ≤0.3); M⁴ is represented by a general formula (5): Nb_(8-π-ψ)Ta_(π)V_(ψ)  (5) (in the formula (5), 0≤π≤8.0 and 0≤ψ0.6); and α, β, and γ satisfy α+β+γ=1.00) and when an arbitrary point in a ternary composition diagram is represented as (α, β, γ), the compound existing within a range surrounded by line segments linking a point A=(0.05, 0.95, 0.00), a point B=(0.70, 0.30, 0.00), a point C=(0.70, 0.00, 0.30), a point D=(0.00, 0.00, 1.00), and a point E=(0.00, 0.90, 0.10) is included as the first component; and as a content ratio relative to a total mass of the first component when the first component is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅, Ta₂O₅, and V₂O₅, the second component comprises at least (a) an oxide of Mn of 0.005% by mass to 3.500% by mass in terms of MnO and (b) one or both of an oxide of Cu and an oxide of Ru.
 4. The dielectric ceramic composition according to claim 3, wherein the first component is a compound existing within a range surrounded by line segments linking a point A′=(0.05, 0.95, 0.00), a point B′=(0.60, 0.40, 0.00), a point C′=(0.70, 0.20, 0.10), a point D′=(0.70, 0.10, 0.20), a point E′=(0.55, 0.00, 0.45), a point F′=(0.40, 0.00, 0.60), a point G′=(0.10, 0.10, 0.80), a point H′=(0.00, 0.00, 1.00), a point I′=(0.00, 0.40, 0.60) a point J′=(0.20, 0.40, 0.40), a point K′=(0.00, 0.70, 0.30), and a point L′=(0.00, 0.90, 0.10) in the ternary composition diagram.
 5. The dielectric ceramic composition according to claim 1, wherein, as the content ratio relative to the total mass of the first component when the first component is converted into CaO, SrO, BaO, TiO₂, ZrO₂, SnO₂, Nb₂O₅, Ta₂O₅, and V₂O₅, the second component comprises one or both of an oxide of Cu of 0.010% by mass or more and less than 0.080% by mass in terms of CuO and an oxide of Ru of 0.050% by mass or more and less than 0.300% by mass in terms of RuO₂.
 6. The dielectric ceramic composition according to claim 1, wherein an oxide of D (D is at least one element selected from Li, Mg, Si, Cr, Al, Fe, Co, Ni, Zn, Ga, Ge, In, W, Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) is included as the second component.
 7. The dielectric ceramic composition according to claim 1, wherein the dielectric ceramic composition comprises a tungsten bronze type crystal phase.
 8. The dielectric ceramic composition according to claim 1, wherein relative dielectric constant at 25° C. is 100.0 or more.
 9. The dielectric ceramic composition according to claim 1, wherein a change rate in electrostatic capacity is within a range of −20.0% to 5.0% in a temperature range of −55° C. to 200° C.
 10. The dielectric ceramic composition according to claim 1, wherein a dielectric loss (tan δ) at 25° C. is 10.0% or less and a dielectric loss (tan δ) at 200° C. is 10.0% or less.
 11. The dielectric ceramic composition according to claim 1, wherein an insulation resistance value at 200° C. is 40 MΩ or more and less than 100 MΩ.
 12. A ceramic electronic component comprising: a dielectric layer formed of the dielectric ceramic composition as claimed in claim 1; and an electrode layer comprising a base metal as a conductive component.
 13. The ceramic electronic component according to claim 12, wherein the base metal is at least one metal selected from nickel and copper.
 14. The ceramic electronic component according to claim 12, wherein a plurality of the dielectric layers and a plurality of the electrode layers are laminated. 